Coordination Chemistry Reviews 256 (2012) 2944–2971

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Coordination Chemistry Reviews

journal homepage: www.elsevier.com/locate/ccr

Review

Syntheses, structures and properties of structurally characterised complexes of

imide-based ligands
Matthew G. Cowan, Sally Brooker ∗
Department of Chemistry and the MacDiarmid Institute for Advanced Materials and Nanotechnology, University of Otago, PO Box 56, Dunedin, 9054, New Zealand

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2945
2. Synthesis of imide ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2946
3. Alkali and alkaline earth metal complexes of imides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2946
3.1. Summary of alkali and alkaline earth metal complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2946
4. Iron complexes of imides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2946
4.1. The discrete complexes [FeII/III (imide)2 ]0/+ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2946
4.2. Complexes assembled from [FeII/III (imide)2 ]0/+ building blocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2948
4.3. Homometallic complexes derived from [FeIII (imide)Xn ] building blocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2951
4.4. Heterometallic complexes of the anionic [FeIII (bpca)(CN)3 ] building block . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2952
4.4.1. Overview of heterometallic complexes of the anionic [FeIII (bpca)(CN)3 ] building block . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2952
4.4.2. Manganese . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2953
4.4.3. Copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2954
5. Copper complexes of imides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2954
5.1. Overview of copper complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2954
5.2. The discrete complex [CuII (bpca)2 ] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2955
5.3. [CuII (bpca)2 ] used as a building block . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2955
5.4. CuII (imide)X·solvents complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2955
5.5. Discrete {[CuII (imide)]2 X} complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2957
5.6. Chain complexes built from [Cu(imide)]+ units . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2960
5.7. Copper complexes with unusual imides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2961
5.8. Heterometallic complexes of [Cu(imide)]+ units . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2961
6. Other first row transition metal ion complexes of imides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2963
6.1. Titanium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2963
6.2. Chromium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2963
6.3. Manganese . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2964
6.4. Cobalt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2964
6.5. Nickel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2965
6.6. Zinc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2966
7. Rhodium, rhenium and platinum complexes of imides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2966
8. Lanthanide complexes of imides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2968
8.1. Overview of lanthanide complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2968
8.2. Lanthanide complexes of imide ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2968

Abbreviations: 1,2-dtcr, 1,2-dithiocroconate; 1,3-dtcr, 1,3-dithiocroconate; 1,3-dtsq, 1,3-dithiosquarate; 4,4 -bipy, 4,4 -bipyridine; 4,4 -dmbipy, 4,4 -dimethylpyridine;
5,5 -dmbipy, 5,5 -dimethylpyridine; AC, alternating current; CFSE, crystal field stabilisation energy; DC, direct current; DA, diacetamide; Dca, dicyanamide; DFT,
density functional theory; DIEDO, diiodoethylenedioxotetrathiavalene; DIET, diiodoethylenedithotetrathiavalene; DMF, dimethylformamide; DMSO, dimethylsul-
foxide; EDTA, ethylenediaminetetraacetic acid; EPR, electron paramagnetic resonance; H, exchange Hamiltonian; Hbpca, bis(2-pyridylcarbonyl)amide; Hbpcam,
bis(2-pyrimidylcarbonyl)amide; Hbmpca, bis(4-methyl-2-pyridylcarbonyl)amide; HbpBuca, bis(4-tBu-2-pyridyl-carbonyl)amide; H3 bcpca, bis(6-carboxypyridine-2-
carbonyl)amine; hfac, hexafluoroacetylacetonate; Hpypzca, N-(2-pyrazylcarbonyl)-2-pyridinecarboxamide; Hdpzca, N-(2-pyrazylcarbonyl)-2-pyrazinecarboxamide; Hpqca,
(2-pyridylcarbonyl)-2-quinolylcarbonyl)diimide; J, coupling constant; Ln, lanthanide ion; Ma, racemic mandelate; Mpa, racemic ␣-methoxyphenylacetate; NHE, normal
hydrogen electrode; S, spin multiplicity; Salcy, N,N -(1,2-cyclohexanediylethylene)bis(salicylideneiminato) dianion; SCE, saturated calomel electrode; SCM, single chain
magnet; SCO, spin crossover; SMM, single molecule magnet; SSCE, silver/silver chloride electrode; tcm, tricyanomethanide; Tp, tris(pyrazolyl)hydroborate; tpy, terpyridine;
TPyT, 2,4,6-tris(2-pyridyl)-1,3,5-triazine; TPymT, 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine; UV–Vis, ultraviolet visible.
∗ Corresponding author. Tel.: +64 3 479 7919; fax: +64 3 479 7906.
E-mail address: sbrooker@chemistry.otago.ac.nz (S. Brooker).

0010-8545/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.ccr.2012.06.004
 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971 2945

8.3. Co-crystallisation of transition metal imide complexes with lanthanide ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2968
8.4. Lanthanide complexes of transition metal/imide metalloligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2969
9. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2970
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2970
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2970

a r t i c l e i n f o a b s t r a c t

Article history: This review details the syntheses, structures and properties of imide-based ligands (phthalimide ana-
Received 31 March 2012 logues have been excluded) and structurally characterised coordination complexes of them. The surveyed
Received in revised form 12 June 2012 imide complexes, including 3D-metal-organic frameworks and 1D-polymers formed from monometallic
Accepted 12 June 2012
building block complexes, exhibit a wide range of interesting properties, including single chain and single
Available online 20 June 2012
molecule magnetism, spin crossover, reversible electrochemistry and luminescence.
© 2012 Elsevier B.V. All rights reserved.
Keywords:
Imide ligand
Monometallic
Trimetallic
Polymetallic
Secondary building units
Heterometallic
Homometallic
Transition metal ion
Lanthanide ion
Single chain magnetism
Spin crossover
Electrochemistry
Structure

1. Introduction Complexes of Hbpca-based imide ligands often feature multiple

secondary/packing interactions in the solid state. These arise due
Since the first structurally characterised imide complexes to the presence of (a) the imide group, which is usually involved in
were reported in 1976 by Lerner and Lippard [1,2] a wealth of hydrogen bonding [3] and/or carbonyl–carbonyl interactions [4],
imide coordination chemistry has been revealed. The main focus and (b) the flat, highly conjugated aromatic rings, which are com-
of these studies has been on complexes of the ligand bis(2- monly involved in parallel offset stacking, C H· · ·␲ and anion· · ·␲
pyridylcarbonyl)amide (Hbpca), however a range of related ligands interactions [5,6]. These packing interactions make imide ligands
has emerged in recent years (Fig. 1). Ligands based on the bpca attractive for producing and manipulating the properties of mag-
anion have two possible binding sites. The N3 donor set consists netically interesting materials.
of the deprotonated, negatively charged imide nitrogen atom and The highly conjugated, and hence flat, nature of the deproto-
the two aromatic nitrogen atoms, whilst the O2 set comprises the nated imide ligands has also led to the predictable formation of
two imide oxygen atoms (Fig. 2). Most complexes feature either a large number of mononuclear complexes of octahedral metal
an N3 or an O2 binding mode, but the combined N3 :␮-O2 binding ions, [MII/III (bpca)2 ]0/+ , which feature the N3 ligand binding mode.
mode is also common, especially in mixed metal 3d–4f complexes Many of these have been designed to be used in the assembly of
(Fig. 2). Other rare binding modes, seen only in one study each, are 1-, 2- and 3-D polymeric complexes which consist of mononu-
described later (Figs. 18, 29 and 38, Sections 5.4, 5.7 and 6.4). clear building blocks bridged by transition metal or lanthanide ions.

O O O O O O O O
R R N N
N N N N N
H H H H
N N N N N N N N

Hbpca R = CH3, Hbmpca Hbpcam Hpypzca

R = tBu, HtBu-bpca
R = C5H5, HPh-bpca

O O O O O O O O

N N N N
H H H H
N N N N N N

diacetamide (DA)
N N O OR' R'O O
Hpqca / Hbqca
R' = H, H3bcpca
R' =CH3, Hbcpc
Hbbpca

Fig. 1. Imide ligands which have been used to produce coordination complexes.
2946 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971
O O O O
N plexes (Fig. 3, route iii) [22]. The proposed mechanism for this
N
N M N
M sponding primary amide, which then reacts with a second amine
N3
M M'
O O O O
N N
H
N N N M N The oxidation of methylene groups situated between aromatic
O2 N3:μ - O2
Fig. 2. Top left: The search fragment used to identify the material included in this
review. Top right: Coordination to the deprotonated N3 donor set (N3 ) is the most
common binding observed. Bottom left: Coordination to the oxygen atoms (O2 )
while the imide nitrogen remains protonated is commonly observed for alkali and
alkaline earth metal ions. Bottom right: A combination of both modes (N3 :␮-O2 ) is
commonly observed for systems where M is a transition metal ion and M is a tran-
sition metal ion or lanthanide ion. Additional but rare binding motifs are shown in
Figs. 18, 29 and 38.
Highlights include single chain [7,8] and single molecule magnets
[9], metal-organic frameworks [10] and materials which display
electrochemical reversibility [11], spin crossover [12] and lumines-
cence [13,14].
This review summarises the preparation and coordination
chemistry of imide ligands reported before June 2011 (Fig. 1). The
review material was identified by means of a Cambridge Structural
Database (Version 5.33)[15,16] search for the fragment shown in
Fig. 2, followed by exclusion of all structures that (a) did not coor-
dinate via either the imide nitrogen and/or the oxygen atom of the
imide or (b) were phthalimide derivatives.
2. Synthesis of imide ligands
The synthesis of the imide ligands Hbpca and Hbpcam (Fig. 1)
was first reported in 1976. They formed unexpectedly during an
investigation into complexes of 2,4,6-tris(2-pyridyl)-1,3,5-triazine
(TPyT) and the pyrimidine analogue (TPymT) (Fig. 3, route i) [1].
Despite the stability of TPyT and TPymT in boiling water and
6 mol L−1 hydrochloric acid, hydrolysis rapidly occurred in the
presence of transition metal ions, particularly copper(II). The result-
ing imide ligands (Fig. 1) were coordinated to the copper ions,
producing [CuII (bpca)2 ] and [CuII (bpcam)2 ] [1,2]. The free ligand
Hbpca was then isolated by treating the copper(II) complexes
with sodium EDTA. Subsequent attempts to coordinate TPyT to
rhodium(III) and ruthenium(II) generated [RhIII (bpca)2 ]PF6 and
[RuII (TPyT)2 ](PF6 )2 [17]. From these results it was determined
that an electron-withdrawing effect, rather than induced angular
strain, was the major factor responsible for metal ion promoted
hydrolysis. Recent studies found that under appropriate reac-
tion conditions copper complexes of triazines can be produced
[18] and that the hydrolysis mechanism can even be reversed
to generate triazine ligands from imine starting materials [19].
Most recently, copper(II)-assisted hydrolysis of 1,3,5-tris(4-alkyl-
2-pyridyl)triazine has been used to produce further imide ligands,
including bis(4-methyl)-2-pyridylcarbonyl)amine (Hbmpca) [20]
and a further series of substituted Hbpca derivatives [8].
Cis- and trans-Pt(NH3 )2 Cl2 have been used as both an ammo-
nia source and a scaffold to facilitate the transformation of two
equivalents of 2-pyridinecarbaldehyde into the corresponding
amide, which is then oxidised by exposure to air to produce
the square planar imide complex [PtII (bpca)Cl] (Fig. 3, route iv)
[21]. In a similar fashion, copper(II) acetate has been used to
combine two amines, ultimately generating copper(II) imide com-
process involves initial oxidation of one amine to the corre-
generating ammonia and the secondary amide, with the latter sub-
sequently oxidised to the imide. This route was used to produce
[CuII (bpca)(OAc)(H2 O)]·H2 O (61%), [CuII (bqca)(OAc)(H2 O)] (58%)
and [CuII (pqca)(OAc)(H2 O)]3 [CuII 2 (OAc)4 (EtOH)2 ]1.5 (52%), which
contain the coordinated pqca anion (Fig. 1). In all three cases the
imide ligands were then isolated quantitatively by removal of cop-
per(II) using sodium EDTA.
rings and amide functionalities has also produced imide complexes
(Fig. 3, route ii) [23–25]. Specifically, the amide ligand N-(2-
picolyl)picolinamide was treated with sodium methoxide and salts
of iron(II) and cobalt(II), producing the complexes [FeIII (bpca)2 ]BF4
(23–45%) and [CoIII (bpca)2 ]ClO4 (50–75%) [24]. The authors deter-
mined that oxidation by atmospheric oxygen proceeded over
around 10 h and could be accelerated by the addition of hydro-
gen peroxide. Similarly, in this research group electrochemistry
was used to observe the partial air oxidation of the amide complex
[CoIII (L1M )2 ]+ (L1M = N-(2-pyridylmethyl)pyrazine-2-carboxamide)
to the analogous imide (Fig. 1) complex [CoIII (pypzca)2 ]+ , however
that complex was not isolated [25]. In principle this method is only
limited by the synthetic availability of the initial amide ligand and
could be used to prepare a wide variety of imide ligands.
Synthetic methods for generating imide ligands without requir-
ing a metal ion have also emerged. Amination of anhydrides, and
oxidation of amides using Dess–Martin Periodinane (DMP) [26],
have been used, but these methods are yet to be applied to the
synthesis of ligands such as those described herein. Other metal-
free routes utilise either the combination of two acid chlorides with
ammonia (Fig. 3, route v) [27] or the combination of an acid chloride
and an amide (Fig. 3, route vi) [13,28]. The wide varieties of starting
materials, straightforward synthesis and large scales possible with
these methods make them extremely attractive for generating a
wide variety of imide ligands. Furthermore, the ability to choose
both an amide and acid chloride starting material allows the highly
controllable preparation of previously uncommon non-symmetric
imide ligands.
3. Alkali and alkaline earth metal complexes of imides
3.1. Summary of alkali and alkaline earth metal complexes
A large number of simple diacetamide (DA, Fig. 1) complexes
with the general formula [M(DA)2–5 ]X1–2 ·(H2 O)0–2 were prepared
with Li+ , Na+ , K+ , Mg2+ , Ca2+ , Sr2+ and Ba2+ and counter-ions includ-
ing NO3 − , ClO4 − , Cl− , Br− and I− [29]. Attempted complexations
were unsuccessful when the metal halide bond was calculated as
greater than 63% ionic character [30] or where the cation:anion
radius ratio was more than 0.78. Infrared studies of these complexes
suggested that the imide nitrogen atom remained protonated and
that the neutral DA ligand coordinated via the imide oxygen atoms.
This was subsequently confirmed by a number of structural studies
(Table 1).
4. Iron complexes of imides
4.1. The discrete complexes [FeII/III (imide)2 ]0/+
A series of mononuclear ‘building block’ com-
plexes, [FeII (bpca)2 ]·H2 O, [FeIII (bpca)2 ](NO3 )·1.67H2 O and
[FeIII (bpca)2 ](ClO4 )·2CH3 CN, was reported in 1993 [12]. The
 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971 2947

TPyT: Y = CH; R,Rii = H

TPymT: Y = N; R,Rii = H

R R''

Y N

N N
R Y Y R
N
N N

R'' R''

1. CuII or RhIII
(i)
2. Na2EDTA

O O O
O O
(vi) (ii)
Cl X NH2 R Y Y R X N
X N H
N N H 1. MII N N
N N
2. O2
R' R'
R' / R'' R'/ R'' HL1M: X = N

(v) (iii)
1. PCl5 1. [Cu(OAc)2]
O 2. NH3 2. Na2EDTA
(iv) H 2N
2 OH 2
1. [PdCl2(NH3)2] N
N

Fig. 3. Reported synthetic routes for obtaining Hbpca and related ligands (R = H, CH3 ; t Bu; Ph; X = CH, N; Y = CH, N); (R = H, COOH, bipyridine). (i) Hydrolysis of symmetric
triazine systems using CuII or RhIII followed by its removal with EDTA. (ii) Oxidation of amide based ligands using CoII or FeII , note however that only the MIII complexes have
been isolated, not the pure ligand. iii) The combination of amines using copper(II) acetate. This has been used to produce symmetric and non-symmetric ligands. (iv) The
combination of aldehydes using trans- or cis- [PtCl2 (NH3 )2 ] (v). Condensation of symmetric carboxylic acids with ammonia via in situ generation of the acid chloride. (vi)
Preparation of the acid chloride followed by reaction with an amide, allowing symmetric or non-symmetric ligands to be produced.

Table 1
Selected information on structurally characterised complexes of DA (Fig. 1): space group, metal ion coordination number and geometry, metal ion to imide oxygen atom
bond lengths.

Complex Space group Coordination Geometry M–Oimide (Å) Reference

number

[Li(DA)2 NO3 ] P-1 5 Trigonal bipyramid 1.987, 2.637 [31]

2.032, 2.068a
[Na(DA)2 Br] Cmca 4 Square planar 2.332, 2.314b [32]
[Na(DA)2 ClO4 ] P21 /c 6 Octahedral 2.385, 2.314 [33]
2.358, 2.337
2.505, 2.492
[K(DA)2 ]I P-1 4 Square planar 2.717, 2.642 [34]
2.661, 2.730
[Mg(DA)2 (H2 O)2 ](ClO4 )2 ·2DA P-1 6 Octahedral 2.041, 2.048c [35]
[Ca(DA)4 ]Br2 C2/c 8 Antiprismatic 2.405, 2.461b [36]
2.425, 2.373b
[Ca(DA)4 ](ClO3 )2 ·H2 O P2/c 8 Square antiprism 2.405, 2.407b [37]
2.402, 2.449b
[Ca(DA)4 ](ClO4 )2 ·DA P2/c 8 Antiprismatic 2.382, 2.449 [38]
2.430, 2.394
2.408, 2.439
2.423, 2.389
[Sr(DA)4 H2 O](ClO4 )2 P21 /m 9 Mono-capped square 2.544, 2.626b [39]
antiprism 2.692, 2.552
2.591, 2.591a
[Ba(DA)5 ](ClO4 )2 P21 /c 10 Symmetrically bicapped 2.80, 2.82 [40]
square antiprism 2.83, 2.91
2.73, 2.84
2.79, 2.89
2.81, 2.74
a
The M–X bond distance of the non-imide donor has not been included.
b
Imide ligands which generate a symmetry equivalent set of O2 donors.
c
Imide ligands which generate two symmetry equivalent sets of O2 donors.
2948 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971
Fig. 4. The crystal structures of [FeII (bpca)2 ]·H2 O (left) and cation of
[FeIII (bpca)2 ](ClO4 )·2CH3 CN (right). Solvent molecules, counterions and hydrogen
atoms have been omitted for clarity.
Source: These figures were generated from data obtained from the CCDC as published
originally in references [12] and [23], respectively.
complexes were prepared in a mixture of water and acetone
by a 2:1 combination of Hbpca with iron(II) sulphate, iron(III)
nitrate and iron(II) perchlorate, respectively. Addition of sodium
hydroxide increased the pH of the reaction solution, promoting
coordination and precipitation of the complexes from solution.
The complex [FeIII (bpca)2 ](ClO4 ) has also been produced by
air oxidation of bis(2-picolyl)amine in the presence of iron(II)
perchlorate [23]. Complexes have also been prepared from
methyl, tert-butyl and phenyl disubstituted ligands (Fig. 1),
producing [FeIII (bpmca)2 ](ClO4 ) [20], [FeIII (t Bu-bpca)2 ]ClO4 and
[FeIII (Ph-bpca)2 ]ClO4 [8].
The analysis of the crystal structures of these complexes is com-
plicated by their spin crossover behaviour (for an introduction
to the field of spin crossover please see reference [41]). Electron
paramagnetic resonance (EPR) and magnetic susceptibility mea-
surements on the iron(II) complex [FeII (bpca)2 ]·H2 O show that it
is mostly low spin but has a residual paramagnetic fraction of 0.18
(2.09 BM) at room temperature which drops to 0.10 (1.53 BM) at
20 K [12]. The nature of the gradual spin crossovers of the two struc-
turally characterised iron(III) complexes, [FeIII (bpca)2 ]X, is anion
dependent. Specifically, the eff of [FeIII (bpca)2 ]NO3 ·1.67H2 O is
3.00 BM at room temperature, dropping to 2.20 BM at 240 K, then
to 1.80 BM, fully low spin, at 20 K. In contrast, the spin crossover of
[FeIII (bpca)2 ]ClO4 ·CH3 CN is incomplete, the eff is 4.4 BM (51% HS)
at 290 K and gradually drops to 3.3 BM at 20 K (25% HS).
The crystal structure of [FeII (bpca)2 ]·H2 O (293 K, Fig. 4)
is typical of [MII/III (imide)2 ]0/+ complexes, with the iron(II)
bound in two approximately perpendicular N3 pockets [12].
The two adjacent, constricted, 5-membered chelate rings of
the bpca anion do not fully ‘wrap around’ the iron(II) ion.
Hence the trans intra-ligand Npy –FeII –Npy angles are ‘pinched’
(163.9◦ and 165.1◦ ), rather than being close to 180◦ . The
geometries of the predominantly low spin iron(III) complexes
[FeIII (bpca)2 ](NO3 )·1.67H2 O (293 K), [FeIII (bpca)2 ](ClO4 )·2CH3 CN
(150 K) and [FeIII (bpmca)2 ](ClO4 )·H2 O·0.5(acetone) (100 K) are
likewise distorted with similar intra-ligand Npy FeIII Npy angles
(163.7–164.4◦ ). The bond lengths were reported as being consis-
tent with low spin iron in all of these structures (Table 2). In all
cases the Fe–Nimide bonds are slightly shorter than the Fe–Npyridine
bonds. The two ligand planes, and hence also the two planes com-
prising the imide nitrogen and two imide oxygen atoms of each
ligand, are approximately perpendicular to one another. This has
significant consequences for the magnetic pathways in complexes
where such mononuclear units are bridged by other metal centres
through the imide oxygen atoms (see later).
The complexes [FeII/III (bpca)2 ]0/+ appear to be air stable as solids
and in solution, and [FeII (bpca)2 ]·H2 O has been used as a mild
reducing agent [11]. The cyclic voltammogram of [FeII (bpca)2 ]
in chloroform shows a quasi-reversible peak at 0.35 V vs a sil-
ver/silver chloride electrode (SSCE). Electrochemical studies of
[FeIII (bpmca)2 ](ClO4 ) in nitromethane show that it undergoes a
reversible one electron process (∼−0.2 V vs Ag/Ag+ ), at a more neg-
ative potential than the [FeII/III (bpca)2 ]0/+ couple (∼0.0 V vs Ag/Ag+
in nitromethane). This indicates that, as expected, the inclusion
of electron donating methyl groups in the imide ligands stabilises
iron(III) relative to the iron(II) oxidation state [20], which may be
why [FeII (bpmca)2 ] has not been reported.
4.2. Complexes assembled from [FeII/III (imide)2 ]0/+ building blocks
The mononuclear unit [FeII (bpca)2 ] has been combined with
[FeIII (H2 O)6 ](ClO4 )3 to prepare black crystals of the discrete
trimetallic complex [FeII (ClO4 )2 [FeIII (bpca)2 ]2 ](ClO4 )2 ·4(CH3 NO2 )
and of the polymeric single chain magnet originally
reported as {[FeII (ClO4 )2 [FeIII (bpca)2 ]](ClO4 )·2.5(CH3 NO2 )·
0.5(CH2 Cl2 )·0.5(H2 O)}∞ (Fig. 5) [11,43], and later reported as
the ·3CH3 NO2 solvate which was investigated as a single molecule
magnet (Tables 2 and 3) [8,42,44]. For an introduction to the field
of single molecule and single chain magnets please see reference
[41]. The nature of the reaction product was controlled by using a
2:1 or 1:1 ratio of [FeII (bpca)2 ] to [FeIII (H2 O)6 ](ClO4 )3 , respectively.
During the synthesis a redox reaction occurs whereby [FeII (bpca)2 ]
is oxidised by [FeIII (H2 O)6 ](ClO4 )3 and the resulting chains are
constructed from alternating [FeIII (bpca)2 ]+ and [FeII (ClO4 )2 ] units
(Fig. 5).
The discrete trimetallic complex consists of two [FeIII (bpca)2 ]+
units bridged via the imide oxygen atoms by one [FeII (ClO4 )2 ] unit.
The central high spin iron(II) ion sits on an inversion centre and
has an octahedral coordination sphere, formed by four imide oxy-
gen atoms in a square plane and capped axially by two ClO4 anions.
The axial FeII –Operchlorate bonds (2.253 Å) are significantly longer
than the FeII –Oimide bonds (2.057, 2.043 Å). The bond lengths of the
iron(III) centre are consistent with a low spin electronic configu-
ration (Table 2). While a study of the properties of this discrete
complex appears to have been overlooked, a significant amount of
attention has been devoted to the polymeric complex, as described
below.
From a structural perspective, the polymeric complex appears
to be a simple extension of the discrete complex. However it has
a 1:1 ratio of the components (rather than the 2:1 ratio of the dis-
crete complex) and it is crystallographically different (P21 /n vs P-1),
with a glide plane generating adjacent repeat units of the poly-
mer. Despite this, the average bond lengths around the high spin
iron(II) centre are similar (FeII –Oimide 2.052 Å and FeII –Operchlorate
2.140 Å), to those in the discrete complex (FeII –Oimide 2.050 Å and
FeII –Operchlorate 2.162 Å or 2.253 Å). On average the FeIII –N bond
length around the low spin iron(II) centre (1.953 Å) is similar to
that in the discrete complex (Table 2). As a result of the sec-
ondary coordination of the building block complex, the imide C O
bond distances lengthen from 1.208 to 1.243 Å. The chains are
magnetically isolated with no intermolecular interactions observed
between them.
The polymeric chain complex, with alternating low spin iron(III)
centres and high spin iron(II) centres, displays the properties of a
single chain magnet (SCM). It was reported in 2005 as being unique
because the SCM properties arise from a twisted arrangement of
easy plane axes along the chain axis, producing a novel type of one-
dimensional Ising system with easy axis anisotropy over the whole
chain which is responsible for the slow reversal of magnetisation,
rather than the typical bistability of the constituent ions [42,45].
 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971 2949

Table 2
Structurally characterised complexes containing the [FeII/III (imide)2 ]0/+ moiety (NB. only the first entry contains Fe in the +2 state within this moiety): selected bond lengths
(Å) and angles (◦ ) pertaining to that particular iron centre (i.e. the one bound within this moiety) in the complex.

Complex Temperature (K) Fe–Nimide Fe–Npyridine Npy –Fe–Npy Npy –Fe–Nimide Reference
(Å) (Å) (◦ ) (◦ )

[FeII (bpca)2 ]·H2 O 293 1.918–1.929 1.929–1.957 165.1 81.7/83.4 [12]

163.9 82.5/81.4
[FeIII (bpca)2 ](NO3 )·1.67H2 O 293 1.908–1.908 1.943–1.971 163.7 80.9/83.2 [12]
164.4 82.4/82.0
[FeIII (bpca)2 ](ClO4 )·2CH3 CN 150 1.915–1.926 1.962–1.980 164.2 82.2/82.1 [23]
163.3 81.7/81.6
III
([Fe (bpmca)2 ](ClO4 )·H2 O·0.5(CH3 )CO)2 100 1.901–1.921 1.963–1.971 164.5 82.4/82.2 [20]
163.1 81.5/89.9
1.895–1.924 1.954–1.963 166.2 83.4/82.8
164.8 82.2/82.2
[FeII (ClO4 )2 (FeIII (bpca)2 )2 ](ClO4 )2 ·4CH3 NO2 213 1.869–1.944 1.960–1.980 162.3 83.8/83.8 [11]
167.5 81.0/81.2
{[Fe (ClO4 )2 (Fe (bpca)2 )](ClO4 )·2.5CH2 Cl2 ·0.5CH3 NO2 ·0.5H2 O}∞
II III
190 1.900–1.905 1.969–1.985 164.6 82.3/82.3 [11]
164.6 82.2/82.4
{[FeII (ClO4 )2 (FeIII (bpca)2 )](ClO4 )·3CH3 NO2 }∞ 200 1.907–1.916 1.967–1.984 164.4 82.5/81.7 [8,42]
164.2 82.8/81.6
{[FeII (ClO4 )2 (FeIII (bmpca))](ClO4 )·2CH3 NO2 ·H2 O}∞ 100 1.879–1.912 1.949–1.969 164.2 82.3/82.4 [8]
164.8 82.2/82.3
{[FeII (ClO4 )2 (FeIII (t Bu-bpca)2 )](ClO4 )·3.5CH3 NO2 }∞ 100 1.907–1.909 1.959–1.980 163.0 81.5/82.1 [8]
164.4 82.0/82.4
{[Fe (ClO4 )2 (Fe (Ph bpca)2 )](ClO4 )·4 EtNO2 }∞
II III
100 1.909–1.913 1.959–1.980 163.8 81.7/82.4 [8]
164.2 82.3/82.3

Fig. 5. The crystal structures of discrete [FeII (ClO4 )2 (FeIII (bpca)2 )2 ](ClO4 )2 ·4CH3 NO2 (left) and polymeric {[FeII (ClO4 )2 (FeIII (bpca)2 )](ClO4 )·2.5CH2 Cl2 ·0.5CH3 NO2 ·0.5H2 O}∞
(right), generated from the same building blocks. Solvent molecules, hydrogen atoms and uncoordinated anions have been omitted for clarity.
Source: These figures were generated from data obtained from the CCDC as published originally in reference [11].

The unique environment provided by the imide building block com-
plexes was the key to obtaining the SCM properties. Specifically,
the ␲-donor character and planar arrangement of the imide oxy-
gen atoms lifts the degeneracy of the t2g orbitals, splitting them
into eg and b2g orbitals, quenching the orbital angular momentum
of the high spin (S = 2) iron(II) ions. Consequently, there is easy-
plane-type anisotropy through the plane of the four imide oxygen
atom donors (Fig. 5). The individual easy-plane spins are coupled
to the adjacent low spin (S = 1/2) [FeIII (bpca)2 ]+ units in the chain
in a ferrimagnetic arrangement.
Mössbauer spectra collected at and above 20 K, with no
externally applied magnetic field, show the expected doublets cor-
responding to the high spin iron(II) and low spin iron(III) centers
(Fig. 6, bottom left). However, on further cooling, two six-line sig-
nals emerge at 3.7 K (Fig. 6, bottom right). No external magnetic
field was applied; rather, these sextets correspond to the iron(II)
and iron(III) centres feeling quasi-static hyperfine fields (of 192 and
335 kOe, respectively) due to the paramagnetic relaxation (rever-
sal of spin) in the chain complex occurring at a rate slower than
that of the Mossbauer timescale (10−7 s). This result, in conjunction
with the magnetic data, was used to estimate a blocking tempera-
ture of 1.3 K and activation energy barrier of 27 K. In further work,
Muon spectroscopy, again without an applied external field, was
used to directly observe the ground spin state of the SCM [46].
These experiments were used to observe the growth of short-range
spin ordering and showed that slow reversal of the spin occurred
below 6 K and at 0.3 K the FeII spin fluctuations were almost entirely
suppressed.
More recent work has shown that the magnetic properties
can be altered by removal and re-adsorption of nitromethane

Table 3
Blocking temperature and selected angles between specified pairs of calculated mean planes for a series of four single chain magnets [8].

Complex Fe· · ·Fe intrachain  a (◦ )  b (◦ )  c (◦ ) TB (K)a

{[FeII (ClO4 )2 [FeIII (bpca)2 ]](ClO4 )·3CH3 NO2 }∞ 5.187(2), 5.195(2) 0.5(3) 80.4(2) 84.7 2.3
{[FeII (ClO4 )2 [FeIII (bmpca)2 ]](ClO4 )·2CH3 NO2 ·H2 O}∞ 5.2155(9)–5.2346(9) 3.1(2), 3.5(2) 84.97 (6), 89.35(6) 89.1 2.3
{[FeII (ClO4 )2 [FeIII (t Bu-bpca)2 ]](ClO4 )·3.5CH3 NO2 }∞ 5.229(1)–5.256(1) 3.7(2) 80.2(1) 83.3 2.8
{[FeII (ClO4 )2 [FeIII (Ph-bpca)2 ]](ClO4 )·4 EtNO2 }∞ 5.201(2)–5.252(2) 17.6(3), 17.9(3) 84.6 (2), 84.4 (2) 86.3 2.0

 a : The two planes comprised of three consecutively numbered imide oxygen atoms around the high spin iron(II) centre e.g. O1, O2, O3 and O2, O3, O4.  b : The two
O C N C O planes around the low spin iron(III) centre.  c : The two planes defined by the O4 imide oxygen atoms around two adjacent high spin iron(II) centres.
a
Blocking temperatures were measured at 997 Hz.
2950 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971

Fig. 6. Properties of the SCM {[FeII (ClO4 )2 (FeIII (bpca)2 )](ClO4 )·3CH3 NO2 }∞ . Top left: The temperature dependence of eff (per dimetallic repeating unit) for a powder sample
() and (inset) for an oriented single crystal in a dc field aligned either along the chain () or perpendicular to the chain (䊉). Solid lines are the theoretical curves. Top right:
Out of phase (m  ) ac magnetic susceptibility vs temperature in a 3.0 Oe ac field oscillating at the indicated frequencies with no applied dc field. Solid lines are a guide for
the eyes. Bottom: 57 Fe Mössbauer spectra acquired at the indicated temperatures.
Source: Reprinted with permission from reference [42]. Copyright 2005 American Chemical Society.

from the crystals of this chain complex, {[(FeIII (bpca)2 )

[FeII (ClO4 )2 ](ClO4 )·3(CH3 NO2 )}∞ [44]. Thermogravimet-
ric analysis at 30 ◦ C and X-ray powder diffraction showed
that all three nitromethane solvent molecules per
[FeII (ClO4 )2 (FeIII (bpca)2 )](ClO4 ) unit can be reversibly removed
and regained (repeated for three cycles). The drying, which causes
small structural changes, has a significant effect on the magnetic
behaviour of the complex, increasing the blocking temperature
by 21% (Fig. 7). Proposed explanations for the significant effect of
drying on the magnetic properties included an alteration to the
easy axis of the SCM. As the easy axis arises from the orthogonal
arrangement of the adjacent easy planes of individual iron(II)
ions (it lies approx. along the intersection of these planes), slight
deviations from that arrangement (as could be caused by solvent
loss) will strongly affect the magnetic behaviour. Alternatively
this structural reorganisation could cause a modification to the
antiferromagnetic interaction between the (S = 2) iron(II) and
(S = 1/2) iron(III) ions within the ferrimagnetically arranged chain,
Fig. 7. The plots of the out of phase m  vs T under zero dc applied
leading to the significant changes in observed magnetic behaviour. field using 5, 25, 100, 500 and 1000 Hz frequencies for {[(FeIII (bpca)2 )
An analogous SCM, {[FeII (ClO4 )(H2 O)FeIII (bmpca)2 ](ClO4 )2 · [FeII (ClO4 )2 ]](ClO4 ).3CH3 NO2 }∞ (left) and {[(FeIII (bpca)2 )[FeII (ClO4 )2 ]](ClO4 )}∞
4CH3 NO2 }∞ , was generated from the methyl substituted complex (right).
[FeIII (bmpca)2 ](ClO4 ) (Figs. 8 and 1, Tables 2 and 3) [20]. There Source: Reprinted with permission from reference [44]. Copyright 2007 Elsevier.
 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971 2951

Fig. 8. Crystal structures of the building block [FeIII (bmpca)2 ](ClO4 )·acetone·2H2 O (left) and SCM {[FeII (ClO4 )(H2 O)[FeIII (bmpca)2 ]](ClO4 )2 ·4CH3 NO2 }∞ (right). Note that
solvent molecules, hydrogen atoms and uncoordinated anions have been omitted for clarity.
Source: These figures were generated from data obtained from the CCDC as published originally in reference [20].

is a significant structural difference at the iron(II) centres: one

of the two coordinated perchlorate ions has been replaced by a
water molecule. However, this difference does not result in any
intermolecular contacts significant enough to compromise the SCM
behaviour. Another difference is that the asymmetric unit contains
two sets of each building block moiety, not just one set as in the
previous chain complex. The complex acts as a SCM below 3 K,
although, in contrast to the original SCM, the interaction between
the S = 2 iron(II) and S = 1/2 iron(III) centres within the chain is
noticeably weakened and the activation energy barrier (estimated
at 19 K) is 8 K lower than in the original SCM.
Recent work has extended this series of SCMs to include
t Bu-bpca and Ph-bpca derivatives (Fig. 1) [8]. The building block

[FeIII (imide2 )]ClO4 complexes have been reported, as have the

polymeric chain complexes {[FeII (ClO4 )(H2 O)[(FeIII (t Bu-bpca)2 )]]
(ClO4 )2 ·(CH3 NO2 )3.5 }∞ and {[FeII (ClO4 )(H2 O)]0.5 [FeII (H2 O)2 ]0.5
[FeIII (Ph-bpca)2 ](ClO4 )2.5 ·(CH3 CH2 NO2 )}∞ (Tables 2 and 3). These
complexes were prepared in an analogous manner to those pre-
viously reported and also display SCM behaviour. The distortions
caused by the various substituents are reflected in the blocking
temperatures of this series (H, 2.3 K; CH3 , 2.3 K; t Bu, 2.8 K; Ph,
2 K; Table 3). The larger substituents generated greater Fe· · ·Fe
interchain separations, specifically 10.011(2), 9.3555(1), 10.686
(2) and 11.774(3) Å for the chain complexes produced with the
bpca, bmpca, t Bu-bpca and Ph-bpca imide ligands, respectively.
The t Bu-bpca chain complex can lose and regain CH3 NO2 solvent,
retaining crystallinity during solvent loss. However, unlike for the
analogous complex of the bpca anion, the process is not completely
reversible. The Ph-bpca chain complex became amorphous upon
drying and lost SCM behaviour. This was the first example of an
SCM transitioning between super-paramagnetic and paramagnetic
states. The study concluded that substitution at the 4-position of
the pyridine ring does not appear to affect the magnetic behaviour
of these chain complexes by electronic effects, but rather by the
structural alterations that result from the substitution (Table 3).
The [FeII (bpca)2 ] unit has also been used to bridge two
[M (hfac)2 ] units, where MII = Fe or Mn and hfac = hexafluoroac-
II
etylacetonate [47]. In the resulting discrete trimetallic
[MII (hfac)2 FeII (bpca)2 MII (hfac)2 ] complexes (Fig. 9), the cen-
tral [FeII (bpca)2 ] unit bridges the terminal metal ions via the
imide oxygen atoms and contains a low spin iron(II) ion. In both
complexes the outer iron(II) or manganese(II) centres are in the
high spin state and these outer metal ions are magnetically inde-
pendent of one another at room temperature. Zero field splitting
of the iron(II) centres occurs below 50 K. The lack of magnetic
communication, when compared to the SCM’s discussed above,
could be attributed to the bridging low spin iron imide complex
Fig. 9. The structure of the [MnII (hfac)2 FeII (bpca)2 MnII (hfac)2 ] complex. Note that
solvent molecules, hydrogen atoms and uncoordinated anions have been omitted
for clarity.
Source: This figure was generated from data obtained from the CCDC as published
originally in reference [47].
being diamagnetic iron(II) (S = 0) rather than paramagnetic iron(III)
(S = 1/2).
4.3. Homometallic complexes derived from [FeIII (imide)Xn ]
building blocks
Building block complexes of the formula [FeIII (imide)Xn ]
include [FeIII (bpca)Cl2 (H2 O)], [FeIII (bpca)Cl2 (EtOH)],
[Fe (bpca)Cl2 (CH3 OH)] and [Fe (bpca)(CN)3 ]− [12,48,49]. These
III III
complexes are all 6-coordinate with the bpca anion coordinated
in the N3 fashion and the remaining binding sites occupied by
Cl− and solvents or by CN− . The chloride or cyanide co-ligands
result in high and low-spin electronic configurations, respectively
(Table 4).
The unit [FeIII (bpca)Cl2 (EtOH)] [48] has been used to sequen-
tially generate an anionic tri-iron(III) complex, crystallised as the
hexa-iron(III) Na2 [FeIII 3 (␮3 -O)(bpca)2 Cl4 (␮2 -OEt)2 ]2 (Fig. 10), then
a mixed valent hepta-iron complex {FeII [FeIII 3 (␮3 -O)(bpca)2 Cl4 -
(␮2 -OEt)2 ](EtOH)2 } [50]. The tri-iron(III) subunit consists of two
[FeIII (bpca)Cl] units connected via a [FeIII 3 (␮3 -O)(␮2 -OEt)2 Cl2 ]
moiety by two ␮2 -bridging ethoxide oxygen atoms and a ␮3 -
bridging oxide. Sodium ions then link two tri-iron(III) subunits
via the imide oxygen atoms, forming the hexa-iron(III) struc-
ture, Na2 [FeIII 3 (␮3 -O)(bpca)2 Cl4 (EtO)2 ]2 . Spin frustration occurs
between the three iron(III) centres in each tri-iron subunit, leading
to an overall spin of S = 3/2 per tri-iron(III) cluster.
The mixed valent hepta-iron cluster is made up of two tri-
iron(III) clusters connected through an iron(II) centre. The central,
2952 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971

Table 4
A selection of bond angles and distances for the FeIII (bpca) moiety in [FeIII (bpca)Xn (solvent)]0/3− and [FeIII (bpca)2 ]X complexes.

Complex Temperature (K) Npy –FeIII –Npy (◦ ) Average FeIII –Npy (Å) Reference
III
[Fe (bpca)Cl2 (H2 O)] 208 154.2 2.120 [12]
[FeIII (bpca)Cl2 (EtOH)] 193 154.0 2.123 [48]
[FeIII (bpca)Cl2 (CH3 OH)] 223 154.0 2.119 [49]
[FeIII (bpca)(CN)3 ]PPh4 295 165.7 1.959 [49]
[FeIII (bpca)2 ]NO3 293 163.7, 164.4 1.958 [12]
[FeIII (bpca)2 ]ClO4 143 163.3, 164.2 1.969 [23]
Na2 [FeIII 3 (␮3 -O)(bpca)2 Cl4 (EtO)2 ]2 200 153.5, 153.0 2.137 [50]
[FeII (FeIII 3 (␮3 -O)(bpca)2 Cl4 (EtO)2 )(EtOH)2 ] 193 150.0, 155.4 2.131 [50]

Fig. 10. The sequential formation of [FeIII (bpca)Cl2 (EtOH)] (top left), then the anionic tri-iron(III) cluster, crystallised as Na2 [FeIII 3 (␮3 –O)(bpca)2 Cl4 (EtO)2 ]2 (top right), then
the mixed valent hepta-iron complex [FeII (FeIII 3 (␮3 -O)(bpca)2 Cl4 (EtO)2 )(EtOH)2 ] (bottom). Solvent molecules, hydrogen atoms and uncoordinated anions have been omitted
for clarity.
Source: These figures were generated from data obtained from the CCDC as published originally in references [48] and [50].

high spin iron(II) centre, Fe(4), is in an octahedral O6 environment
made up of four imide oxygen atoms in a square plane and two
axial ethanol molecules (FeII O = 2.090(3)–2.113(4) Å). The ethanol
molecules make hydrogen bond interactions with the adjacent
uncoordinated imide oxygen atoms (O3 and O4). Experimentally
the hepta-iron complex has a ground state spin of S = 12/2, higher
than that expected from ferromagnetic coupling of two tri-iron(III)
units (S = 3/2) and a high spin iron(II) centre (S = 4/2) (STotal = 10/2).
As there are no intermolecular interactions observed in the crystal
structure it was concluded that the magnetic interaction responsi-
ble for generating this unusually high ground spin state lies within
the hepta-iron complex, perhaps due to a change in the ground-
state spin within the tri-iron(III) subunit.
The anionic building block [FeIII (bpca)(CN)3 ]− has a slightly
distorted octahedral geometry around the low spin iron(III)
centre and was first crystallised with a PPh4 + counterion [49].
The complex has been used to produce the charge transfer
salts (DIET)2 [FeIII (bpca)(CN)3 ] and (DIEDO)2 [FeIII (bpca)(CN)3 ]
(Fig. 11) by co-crystallisation with the radical organic units DIET
(diiodoethylenedithotetrathiavalene) and DIEDO (diiodoethylene-
dioxotetrathiavalene) [51]. Crystal structures of the salts reveal
that the organic and inorganic units are packed in alternate layers.
The layers are connected by interactions between the iodine atoms
of DIET and DIEDO and the oxygen atoms of coordinated bpca
anions and nitrogen atoms of the coordinated cyanide (Fig. 11).
The salt formed with DIET acted as a semi-conductor at room tem-
perature. The salt formed with DIEDO is weakly metallic at room
temperature, with large antiferromagnetic coupling between the
radial DIEDO units, but it becomes a semiconductor below 270 K.
4.4. Heterometallic complexes of the anionic [FeIII (bpca)(CN)3 ]
building block
4.4.1. Overview of heterometallic complexes of the anionic
[FeIII (bpca)(CN)3 ] building block
The mono-anionic [FeIII (bpca)(CN)3 ] building block, described
in Section 4.3, has been combined with metal ion ‘linkers’ to pro-
duce a variety of discrete and polymeric networks. The coordinated
 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971 2953

Fig. 11. The alternate organic and inorganic layers of the semiconductor formed from [FeIII (bpca)(CN)3 ] anions and DIET radicals, highlighting the connections between them
(dotted lines). Hydrogen atoms have been omitted for clarity.
Source: This figure was generated from data obtained from the CCDC as published originally in reference [51].

cyanides provide ‘spare’ nitrogen donors that can potentially bind
to other metal ions, and, when combined with the propensity of
imide ligands to promote secondary interactions, this has led to a
variety of polymeric and mixed metal structural motifs. DFT cal-
culations have indicated that the unpaired electron density on the
iron(III) centre is held in a dxy orbital defined by the plane of the
three mer-coordinated cyanide ligands [49]. The structures and
properties of these motifs are described below.
4.4.2. Manganese
Combination of the [(FeIII (bpca)(CN)3 )] anion with man-
ganese(II) was done with the goal of making a one-dimensional
ferrimagnetic chain of the low spin iron(III) (S = 1/2) and high
spin manganese(II) (S = 5/2) centres. The discrete trimetallic com-
plex {[FeIII (bpca)(CN)3 ]2 MnII (CH3 OH)2 (H2 O)2 }·2H2 O (Fig. 12) was
obtained from slow evaporation of a water/methanol solution of
two equivalents of [(FeIII (bpca)(CN)3 )]Bu4 N and one equivalent of
manganese(II) chloride tetrahydrate [52]. The manganese(II) centre
bridges the iron(III) building blocks via trans cyanide interactions,
rather than via the imide oxygen atoms. The asymmetric unit con-
tains two molecules, one with cis-coordinated water molecules
and cis-coordinated methanol molecules (Fig. 12), the other has
these trans-coordinated (Fig. 12). The magnetic data show that
the iron(III) centres remain low spin following coordination to the
manganese(II) centre. The magnetic behaviour was modelled as
antiferromagnetic coupling between the high spin manganese(II)
centre and each of the two low spin iron(III) centres (J = –3.28 cm−1 )
with no coupling occurring between the two terminal iron(III) cen-
tres H = −2JSMn (SFe1 + SFe2 ).
The polymeric structure of {[FeIII (bpca)(CN)3 MnII (H2 O)3 ]-
[FeIII (bpca)(CN)3 ]·3H2 O}∞ is shown in Fig. 13 [49]. The
[FeIII (bpca)(CN)3 MnII (H2 O)3 + ]∞ cation repeats, by a centre of
inversion, forming a double-stranded, cyanide-bridged, cationic
chain, which is connected to the [FeIII (bpca)(CN)3 ] anions via a
complex hydrogen bonding network involving the solvent water
molecules. All of the iron(III) centres are low spin, and DFT calcula-
tions suggest a combination of minor ferromagnetic and dominant
antiferromagnetic coupling between the low spin iron(III) and
high spin manganese(II) centres. Lack of an appropriate model
for describing heterometallic chain complexes prevented a more
detailed evaluation of the magnetic coupling.
Two one-dimensional zig-zag chain complexes,
[(MnIII (Salcy))(FeIII (bpca)(CN)3 )]∞ were prepared using
the (R, R) and (S, S) enantiomers of Salcy (N,N -(1,2-
cyclohexanediylethylene)bis(salicylideneiminato) dianion)
(Fig. 14) [53]. The repeat units of the chain are generated by
translation along the a axis. Again, it is the two axial cyanide lig-
ands, not the imide oxygen atoms, of the anionic [FeIII (bpca)(CN)3 ]
which bridge the [MnIII (Salcy)] cations, via the axial sites of the
manganese(III) ion (all four equatorial sites are occupied by the
Salcy dianion). Both iron(III) and manganese(III) coordination
spheres are distorted octahedral. As expected, the manganese(III)
centres present a Jahn–Teller distortion (TRR = 0.838; TSS = 0.830)
[54]. Both enantiomeric forms display ferroelectric hysteresis, i.e.
hysteretic altering of electric polarisation in response to an applied
coercive field. Polarisation of the local distortions, which would
interfere in electronic communication along the chain, is proposed
as the reason for this observation.

Fig. 12. The structure of one of the two molecules in the asymmetric unit of the discrete trimetallic complex [(FeIII (bpca)(CN)3 )2 MnII (CH3 OH)2 (H2 O)2 ]·2H2 O. Note that the
secondary coordination occurs through the coordinated cyanides, rather than the imide oxygen atoms. Solvent molecules and hydrogen atoms have been omitted for clarity.
Source: This figure was generated from data obtained from the CCDC as published originally in reference [52].
2954 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971

Fig. 13. The structure of the cation of the infinite, heterometallic, double-stranded chain complex {[FeIII (bpca)(CN)3 MnII (H2 O)3 ][FeIII (bpca)(CN)3 ]· 3H2 O}∞ . Hydrogen atoms,
solvent molecules and [FeIII (bpca)(CN)3 ] anions have been excluded for clarity.
Source: This figure was generated from data obtained from the CCDC as published originally in reference [49].

Fig. 14. The one-dimensional ‘zigzag’ chain complex (S, S)-{[MnIII (Salcy)][FeIII (bpca)(CN)3 ]}∞ . Solvent molecules and hydrogen atoms have been excluded for clarity.
Source: This figure was generated from data obtained from the CCDC as published originally in reference [53].

4.4.3. Copper
A bridging unit containing copper(II) has been used to pre-
pare the complex {[FeIII (bpca)(CN)3 ][CuII (H2 O)2 (CN)2 ]·1.5H2 O}∞
[52]. The [FeIII (bpca)(CN)3 ]− anion links the copper(II) centres
through an equatorial and an axial cyanide and the structure was
described as a one-dimensional chain. The shortest intramolecular
distances for Cu· · ·Cu, Fe· · ·Cu and Fe· · ·Fe are 7.263, 4.964, 6.702 Å,
respectively and the shortest intermolecular distances are 11.214,
7.205 and 7.938 Å, respectively. For the modelling of the tempera-
ture dependent and field dependent magnetic measurements, the
system was treated as a uniform CuII /FeIII chain: ferromagnetic
intra- and interdimeric exchange constants, 7.9(3) and 1.03(2) cm−1
respectively, were obtained.
A right-handed helical chain {[FeIII (bpca)(CN)3 ][CuII (bpca)
(H2 O)]·H2 O}∞ has been reported (Fig. 15) [52]. Surprisingly, circu-
lar dichroism measurements on 40 individual crystals from each of
the two batches all exhibited a negative Cotton effect at max = 450
and 625 nm, indicating an enantiomeric excess despite starting
from achiral reagents. The chain structure is constructed from
[FeIII (bpca)(CN)3 ] anions and [CuII (bpca)(H2 O)] cations connected
into dimers via a cyanide bridge (Cu(1) N6 1.953 Å) in the plane
of both bpca− ligands. A second, weaker interaction (Cu(1A)· · ·N5
2.632 Å) connects these dimers into the helical chain structure.
Attempts to model the magnetism as either dimers or chains did not
accurately account for the antiferromagnetic magnetic behaviour
observed for the complex.
5. Copper complexes of imides
5.1. Overview of copper complexes
The imide coordination chemistry of copper is dominated
by copper(II) complexes of Hbpca. The mononuclear complex
[CuII (bpca)2 ] has been reported, however unlike the analogous
[FeII/III (bpca)2 ]0/+ it has not been used to produce a variety of coor-
dination polymer materials. Instead, copper(II) imide complexes
mostly feature only one bound imide anion per copper centre, and
take two main forms: discrete mononuclear [CuII (bpca)X], where
X− does not bridge to another complex; and discrete dinuclear
[CuII (bpca)XCuII (bpca)], where X2− bridges the two copper(II) cen-
tres to form a dimer. Complexes of the form [CuII (bpca)X] have also
been used as building blocks to produce a variety of discrete and
polymeric heterometallic complexes. As a consequence of the use
of copper(II) in imide synthesis (Section 1), imide complexes of cop-
per display the most variety in ligand design. Indeed many Hbpca
ligand variants are only reported as complexes of copper.
 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971
Fig. 15. The structure of the chiral chain complex
[(FeIII (bpca)(CN)3 )(CuII (bpca)(H2 O))·H2 O]∞ , oriented such that the chain runs
into and out of the page. The chain is made up of [Fe (bpca)(CN)3 ]− and
III
[CuII (bpca)(H2 O)]+ dimers connected by a FeIII –CN–CuII bond which repeats by
symmetry (dashed lines; Cu(1A)· · ·N(5) 2.632 Å). Solvent molecules and hydrogen
atoms have been excluded for clarity.
Source: This figure was generated from data obtained from the CCDC as published
originally in reference [52].
5.2. The discrete complex [CuII (bpca)2 ]
The structure of [CuII (bpca)2 ]·H2 O (Fig. 16) [55] is similar to that
of [FeII/III (bpca)2 ]0/+ , but it differs in that the geometry around the
six coordinate copper(II) ion is significantly distorted away from
octahedral due to the Jahn–Teller effect. The Cu–N bond lengths
are longer along the z axis (CuII –Npy = 2.29–2.30 Å) compared to the
x and y axes (CuII –Npy = 2.08, 2.09 Å). Hence, unlike in the iron(II)
and iron(III) analogues (Table 2), one ligand is very different to
the other. EPR spectroscopy showed that a considerable amount
of the unpaired electron spin was transferred onto the ligands.
This suggests that [CuII (bpca)2 ] units, in combination with an
Fig. 16. A ball and stick representation of [CuII (bpca)2 ]·H2 O. Note that solvent
molecules and hydrogen atoms have been excluded for clarity.
Source: This figure was generated from data obtained from the CCDC as published
originally in reference [55].
2955
appropriate bridging metal ion, would be excellent building blocks
for facilitating electronic communication, with structures like those
exemplified above in the iron section of this review (Section 4.2).
However, the complex [CuII (bpca)2 ] has only been used as a build-
ing block for the construction of one extended complex (Section
5.3) [47]. This may be due to the combined effects of the Jahn–Teller
distortion on one of the fully conjugated bpca anions and the labil-
ity of copper(II) leading to disassembly of the [CuII (bpca)2 ] unit
in solution, preventing predictable and/or controlled construction
of larger assemblies. Another potential pitfall is that, as copper(II)
gains little crystal field stabilisation energy (CFSE) from being in an
octahedral geometry, during such secondary assembly reactions
transmetalation of copper(II) by metal ions such as iron(II) and
iron(III) can occur, especially as these are likely to have a low spin
electronic configuration and hence even greater CFSE [47].
5.3. [CuII (bpca)2 ] used as a building block
The only example of the [CuII (bpca)2 ] unit being used as a
building block is the complex [MnII (hfac)2 CuII (bpca)2 MnII (hfac)2 ],
which is isostructural to the iron(II) complex
[MnII (hfac)2 FeII (bpca)2 MnII (hfac)2 ] described earlier, in Sec-
tion 4.2 (Fig. 9) [47]. The copper(II) ion in the N6 pocket has an
average bond length of 2.134 Å compared to Fe–N = 1.958 Å in the
low spin iron(II) analogue (Fig. 9). Unlike the rest of the man-
ganese(II) and nickel(II) analogues (Sections 6.3 and 6.5), there was
no interaction between the CuII and MnII centres. For the reasons
discussed above (see Section 5.2), attempts to use [CuII (bpca)2 ] to
bridge [FeII (hfac)2 ] units led to transmetallation, with a low spin
iron(II) ion replacing the copper(II) ion and forming the all-iron(II)
imide complex.
5.4. CuII (imide)X·solvents complexes
Many complexes of the formula [CuII (bpca)X] have resulted
from the hydrolysis of TPyT (Fig. 3), in the presence of differ-
ent co-ligands. However deliberate synthesis from the isolated
imide ligand offers the opportunity to choose the co-ligands that
will occupy the remaining coordination sites of the three coor-
dinate copper(II) ion in the [CuII (bpca)]+ moiety. The formulae
and selected bond distances and angles of the mononuclear com-
plexes reported to date are summarised in Table 5. In all cases
the bpca anion is meridionally bound through the N3 donor set.
The significant deviations from ideal square-based geometries, as
exemplified here by the trans Npy -Cu-Npy angles of 153.0–164.8◦
are due to the small bite angle (77.0–82.6◦ ) of the two adjacent
5-membered chelate rings imposed by the bpca anion (Table 5).
The coordination numbers and geometries of the copper(II) centres
in these monometallic [CuII (imide)X] complexes vary: 4 coordi-
nate are distorted square planar, 5 coordinate are distorted square
based pyramids, and 6 coordinate are distorted octahedra. The
examples selected for discussion are: [CuII (bpca)(tptz)](CF3 SO3 )
[56], [CuII (bpca)(Cl)(NCO)] [27] and [CuII (bpca)(H2 O)2 ]NO3 [57]
(Fig. 17). These include uncoordinated anions, coordinated anions
and a hydrogen bonded network, respectively.
As the bpca anion is fully conjugated it is expected to remain
planar when coordinated. However, in all of these [CuII (bpca)]+
complexes the bpca anion is better described as being “hinged”
along the CuII Nimide bond, comprising two planar ‘halves’ which
intersect at an angle of 6–8◦ [58,59]. Each half is made up of one
pyridine ring, the adjacent carbonyl group and the imide nitrogen
atom. When the ligand is considered as being made up of two indi-
vidual planes the atoms within the two halves of the ligand deviate
by, at most, 0.012 Å from their respective planes, whereas when
the plane is comprised of the whole ligand, several atoms deviate
significantly from that plane (by, at most, 0.689 Å [59]).
2956 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971

Table 5
A list of monometallic [CuII (imide)X] complexes containing the [CuII (bpca)]+ or [CuII (bpcam)]+ moiety and selected bond lengths and angles pertaining to the coordination
of the imide ligand around the copper(II) ion.

Complex CuII –Nimide (Å) CuII –Npy (Å) Npy –CuII –Npy (◦ )a Npy –CuII –Nimide (◦ )a Reference
II b,c
[Cu (bpca)2 ]·H2 O 1.960, 1.997 2.084–2.305 160, 153 80/80, 77/78 [55]
[CuII (bpca)(C5 NH5 CONH2 )(ClO4 )] 1.931 2.018/2.017 162.0 82.0/82.1 [56]
[CuII (bpca)(C5 NH5 CONH2 )(CF3 SO3 )] 1.935 2.016/2.022 163.5 81.5/82.4 [59]
[CuII (bpca)(TpyT)](CF3 SO3 )c 1.956 2.047/2.055 162.8 81.3/81.5 [59]
[CuII (bpca)(H2 O)2 ](NO3 ) 1.938 1.994/1.996 163.8 81.87/81.98 [57]
[CuII (bpca)(Cl)(NCO)] 1.952 2.022/2.026 161.9 80.7/81.5 [27]
[CuII (bpca)(Br)]d 1.928 2.011/2.011 164.2 82.1/82.1 [18]
[CuII (bpca)(I)]d 1.936 2.020/2.020 164.5 82.5/82.5 [18]
[CuII (bpca)(2Cl C6 H4 CO2 )(H2 O)] 1.947 2.012/2.014 161.9 81.5/81.7 [61]
[CuII (bpca)(3Cl C6 H4 CO2 )]d 1.928 2.000/2.002 164.8 82.3/82.5 [61]
[CuII (bpca)(4Cl C6 H4 CO2 )(DMF)] 1.950 2.012/2.018 163.3 81.89/81.65 [61]
[CuII (bpca)(C5 NH5 CO2 )]·2(H2 O) 1.952 2.046/2.047 159.9 80.87/80.94 [62]
[CuII (bpca)(CH3 CO2 )(H2 O)2 ]·H2 Oc 1.947 1.998/2.000 162.0 81.6/82.3 [60]
[CuII (bpca)(NCS)(H2 O)] 1.94 2.00/2.01 162.0 81.5/81.8 [58]
[CuII (bpcam)(H2 O)3 ]NO3 c 1.938 2.002/2.020 163.5 81.57/82.01 [2]
[CuII (bpcam)(H2 O)2 ]ClO4 ·3H2 O 1.940 2.011/2.011 162.6 81.77/81.85 [63]
[CuII (bpcam)(tcm)(H2 O)] 1.935 2.035/2.036 162.6 81.20/81.60 [64]
[CuII (bpcam)(tcm)(H2 O)]·2H2 O 1.937 2.019/2.027 161.9 81.47/81.60 [64]
[CuII (bpcam)(CN)(H2 O)] 1.950 2.036/2.036 160.4 80.51/80.78 [65]
[CuII (bpcam)(N3 )(H2 O)] 1.954 2.031/2.027 160.2 80.70/81.30 [65]
[CuII (bpcam)(NCS)(H2 O)] 1.936 2.019/2.028 161.1 81.03/81.39 [65]
[CuII (bpcam)(dca)(H2 O)] 1.941 2.024/2.045 161.4 81.09/81.12 [65,66]
[CuII (bpcam)(ma)] 1.931 1.999/2.005 163.3 82.6/82.0 [67]
[CuII (bpcam)(mpa)(H2 O)]·0.5H2 O·0.5CH3 OH 1.933 2.009/2.014 163.5 81.7/81.75 [67]

Unless otherwise noted the geometry of the copper(II) ion is square pyramidal.
a
Intraligand.
b
Evident Jahn–Teller distortion.
c
Six-coordinate complex.
d
Four-coordinate complex.

The crystal packing of these complexes often shows head to molecules (Fig. 17) [58,59,61,62]. An unusual feature is present
tail carbonyl–carbonyl interactions [60], stacking of pyridine rings in the crystal packing of [CuII (bpca)(H2 O)2 ](NO3 )·2H2 O [57] and
[27,61] and extensive hydrogen bonding networks between the [CuII (bpca)(3Cl C6 H4 CO2 )] [61]. In [CuII (bpca)(H2 O)2 ](NO3 )·2H2 O,
imide oxygen atoms and coordinated and uncoordinated solvent in the sixth potential coordination site of the copper(II) centre, a

Fig. 17. The structures of [CuII (bpca)(tptz)](CF3 SO3 ) (left), [CuII (bpca)(H2 O)2 ]NO3 ·2(H2 O) (right) and [CuII (bpca)(Cl)(NCO)] (bottom). Anions and non-acidic hydrogen atoms
have been omitted for clarity.
Source: These figures were generated from data obtained from the CCDC as published originally in references [27], [57] and [59].
 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971
Fig. 18. The structure of [CuII (bpca)(3Cl C6 H4 CO2 )] depicting a weak side-on imide
C O· · ·CuII interaction between adjacent complexes. Hydrogen atoms have been
omitted for clarity.
Source: This figure was generated from data obtained from the CCDC as published
originally in reference [61].
very weak side-on interaction (3.302 Å) occurs with the imide oxy-
gen atom of an adjacent complex. In [CuII (bpca)(3Cl C6 H4 CO2 )]
(Fig. 18) a similar side-on carbonyl copper(II) interaction occurs
[Cu(1) O(2A) = 2.7189 Å], with the oxygen atom occupying the api-
cal site of a square based pyramid. While the imide oxygen atoms
are commonly observed to coordinate to a single metal centre in
an in-plane bidentate fashion, these monodentate side-on interac-
tions provide another type of weak coordination mode for imide
type ligands. Another notable feature of these side-on CuII · · ·Oimide
interactions is the deviation of the imide oxygen atom, i.e. O(2) in
Fig. 18, out of the plane of the adjacent pyridine ring towards the
copper(II) centre, Cu(1B), by 0.391 Å in this case.
UV–vis studies have been used to show that the complex
[CuII (bpca)(C5 NH5 CONH2 )(ClO4 )] becomes [CuII (bpca)(H2 O)3 ]+ in
solution. The lability of the co-ligands in copper(II)/imide com-
plexes is an important consideration when designing molecular
building blocks for higher order structures [56]. With regard to the
stability of these complexes, studies examining the acid–base equi-
libria of the complex [CuII (bpca)(H2 O)2 ](NO3 ) concluded that the
compound remained intact in the pH range 3–7, however outside
this pH range either protonation or deprotonation of the complex
occurs. Comparison of the UV–vis spectra at pH values of 1.5 and 7
showed that the [CuII (bpca)]+ unit remained intact so protonation
of the complex did not result in the imide ligand dissociating [57].
Electrochemical studies of the complex
[CuII (bpca)(2Cl C6 H4 CO2 )(H2 O)] showed an irreversible reduc-
tion, at −0.78 V in acetonitrile or −0.434 V in dimethylformamide,
vs NHE [61]. This was assigned as CuII → CuI , and the irreversibility
was attributed to the CuI complex being unstable, resulting in
decomposition. The highly negative reduction potential showed
that, as expected, the copper(II) oxidation state is significantly
stabilised by coordination to the imide anion, in comparison to
free CuII (E0 Cu(II) /Cu(I) = 0.153 V) [68].
Copper complexes of Hbpcam were also originally produced
from the hydrolysis of the corresponding triazine (Fig. 3). Indeed
the complex [CuII (bpcam)(H2 O)3 ]NO3 was the first reported
structure of an imide complex [1,2]. The structural characteristics
of Hbpcam complexes are similar to those of Hbpca complexes
(Table 5). When coordinated, the bpcam anion is also best described
as two planes, however the dihedral angle between these planes
(3–13◦ ) varies more from complex to complex than was the case
2957
Fig. 19. The structure of [CuII 2 (bpca)2 (H2 O)2 (SO4 )]·H2 O where the sulphate anion
forms a three atom bridge between the copper(II) centres. Hydrogen atoms not
involved in hydrogen bonding (dashed lines) have been excluded for clarity.
Source: This figure was generated from data obtained from the CCDC as published
originally in reference [63].
for the coordinated bpca anion (6–8◦ ). The complexes have the
same propensity to form extended hydrogen bonded networks
through the imide oxygen atoms; interestingly the uncoordinated
pyrimidine nitrogen atoms are not involved.
5.5. Discrete {[CuII (imide)]2 X} complexes
The synthesis of discrete dinuclear {[CuII (imide)]2 X} complexes
has been performed both directly from a mixture containing cop-
per(II) nitrate and TPyT (Fig. 1) and from the labile building block
[CuII (imide)(H2 O)2 ]NO3 , by the addition of a divalent anion salt.
The coordinated water can be substituted by the bridging dian-
ion X2− under very mild reaction conditions, i.e. short periods
of stirring at room temperature. Therefore the majority of these
bridged complexes have been prepared by either slow evapora-
tion of a reaction solution or slow diffusion together of solutions
containing the reactants. Particular attention has been paid to mag-
netostructural relationships in the resulting dimetallic complexes:
the [CuII (imide)]+ moiety is a useful cationic building block to
examine the nature of the magnetic pathways provided by the var-
ious dianionic linkers. In all cases the unpaired electron density is
determined to be lying in an equatorial dx2 −y2 metal centred orbital
where the x and y axes (the equatorial plane of the copper(II) cen-
tre) are approximately defined by the imide and aromatic nitrogen
atoms of the imide ligand. In all but three of the complexes exam-
ined here (Figs. 20 and 26), the dianion provides the fourth donor
in this plane.
Tetrahedral dianions bridge the [CuII (imide)]+ units in
two ways, either via three atoms (i.e. CuII –O–A–O–CuII ),
as in the cases of [CuII 2 (bpca)2 (H2 O)2 (AO4 )]·H2 O, A = W
[69], Mo [69], and [CuII 2 (bpcam)2 (H2 O)2 (AO4 )]·H2 O, A = S
(Fig. 19) [63], or via a single oxygen atom (CuII –O–CuII )
in the cases of [CuII 2 (bpca)2 (H2 O)3 (AO4 )]·H2 O where
A = S or Cr (Fig. 20) [70]. In contrast, in the complex
[CuII (bpcam)(H2 O)2 ][CuII (bpcam)(H2 O)(SO4 )], sulphate is
observed to coordinate but not bridge [63]. In this case, the
coordination mode obtained appears to depend on the source of
sulphate: either CuSO4 (both) or Na2 SO4 (non-bridging).
In the complexes where the [CuII (bpca)]+ units are linked by
three atom bridges provided by tungstate, molybdate or sulphate,
the copper(II) ions adopt a square pyramidal geometry with an
oxygen atom of the anion and the imide-N3 pocket making up
the equatorial plane, which is capped by a coordinated water
2958 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971
Fig. 20. The structure of [CuII 2 (bpca)2 (H2 O)3 (CrO4 )]·H2 O. Non-acidic hydrogen
atoms have been omitted for clarity.
Source: This figure was generated from data obtained from the CCDC as published
originally in reference [70].
molecule at the apical position (Fig. 19) [69]. The anions provide
three atom bridges between the two copper(II) centres (CuII · · ·CuII
distances of 5.572, 5.550 and 5.494 Å, respectively). The resulting
discrete dicopper(II) complexes are further connected through a
hydrogen bonding network involving all available oxygen atoms
except O(6). Magnetic coupling between the pair of copper(II) cen-
tres varies widely with anion, from weak ferromagnetic coupling
for tungstate (J = 0.557 cm−1 ), to antiferromagnetic coupling for
molybdate (J = −77.2 cm−1 ), to weak antiferromagnetic coupling for
sulphate (J = –7.0 cm–1 ) (H = −JS1 ·S2 ).
The dimetallic complexes [CuII 2 (bpca)2 (H2 O)3 (SO4 )]·H2 O and
[CuII 2 (bpca)2 (H2 O)3 (CrO4 )]·H2 O are isostructural [70]. Both com-
prise a square pyramidal and an octahedral copper centre bridged
by a single oxygen atom of the oxo-anion, with the whole dicop-
per(II) molecule in the asymmetric unit (Fig. 20). Again, the oxygen
atoms are involved in a large number of hydrogen bonds. The
intramolecular CuII · · ·CuII distances are 3.747 and 3.660 Å for the
Fig. 21. The oxalate bridged complex [CuII 2 (bpca)2 (H2 O)2 (C2 O4 )]·2H2 O. Non-acidic hydrogen atoms have been omitted for clarity.
Source: This figure was generated from data obtained from the CCDC as published originally in reference [70].
sulphate and chromate complexes, respectively, and the shortest
intermolecular CuII · · ·CuII distances are 6.923 and 6.971 Å, respec-
tively. The antiferromagnetic coupling propagated through the
single atom bridges is weak due to the bridging anion occupying
an equatorial site on the square pyramidal copper centre, but an
axial site on the octahedral copper centre (sulphate J = −0.6 cm−1 ;
chromate J = −1.6 cm−1 ). (H = −JS1 ·S2 ).
The organic acids oxalate, squarate and croconate have also been
used as linkers between [CuII (imide)]+ units. The pair of structurally
characterised oxalate complexes [(CuII (bpca))2 (H2 O)2 (C2 O4 )] [71]
and the dihydrate [(CuII (bpca))2 (H2 O)2 (C2 O4 )]·2H2 O [70] (Fig. 21)
feature octahedral copper(II) centres, with half of the complex
in the asymmetric unit and the other half generated by a cen-
tre of inversion. The imide oxygen atoms of the coordinated bpca
anion are heavily involved in intermolecular hydrogen bonding.
In both structures the planar bis-bidentate oxalate anion binds
to each of the two copper(II) centres via both an axial and equa-
torial position, bridging them (intramolecular CuII · · ·CuII 5.631 vs
5.422 Å for the dihydrate). In both cases the plane of the bridg-
ing oxalate anion is almost at right angles (80.6◦ vs 83.6◦ for
the hydrate) to the equatorial plane of the copper(II) ion. Hence
it is not surprising that both complexes display only a very
weak ferromagnetic interaction between the copper(II) centres,
with the non-hydrated form displaying the slightly stronger cou-
pling (J = + 1.1 vs +1.0 cm−1 ). (H = −JS1 ·S2 + S1 DS2 ). The analogous
complex [(CuII (bpcam))2 (H2 O)2 (C2 O4 )] adopts a similar structure,
however the oxalate and copper equatorial planes are some-
what less orthogonal to one another (69.2◦ ) and the CuII · · ·CuII
distance is slightly longer (5.677 Å). Weak ferromagnetic cou-
pling (J = +0.75 cm−1 ) was also observed for this analogue [72].
(H = –JS1 ·S2 ).
In the dimetallic complex [(CuII (bpca))2 (H2 O)2 (C4 O4 )] (Fig. 22)
the equatorial sites of the two copper centres are bridged by a pla-
nar squarate anion. As in the oxalate structures, only half of the
complex is in the asymmetric unit and the other half is generated
by a centre of inversion.
The plane of the anion bridge is close to perpendicular (85.5◦ )
to the equatorial plane of the copper(II) centre. The observed
CuII · · ·CuII distance is 7.833 Å, far longer than in the oxalate
complex, as expected for this longer bridge. Unsurprisingly,
magnetic studies show there is no coupling via the squarate
bridge [73]. In contrast, in the structurally characterised ana-
logue [(CuII (bpcam))2 (H2 O)4 (C4 O4 )]·10H2 O, whilst the metal ions
are held at the same separation (7.819 Å), the copper equatorial
plane and that of the squarate are further from being orthogonal
 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971 2959

Fig. 22. The structure of two [CuII (bpca)(H2 O)]+ units linked by a squarate anion. Non-acidic hydrogen atoms have been omitted for clarity.
Source: This figure was generated from data obtained from the CCDC as published originally in reference [73].

to one another (67.8◦ ). Weak ferromagnetic coupling constants of
J = +0.75 cm−1 (anhydrous) and J = +1.3 cm−1 (·10 H2 O) are observed
[72]. (H = −JSA ·SB ).
In the complex [CuII 2 (bpca)2 (C5 O5 )]·3H2 O (Fig. 23) the entire
dimetallic complex is in the asymmetric unit [74]. Both the square
pyramidal, Cu(2), and octahedral, Cu(1), copper(II) centres again
feature an N3 -coordinated imide ligand in the equatorial plane.
The planar croconate anion is triply bridging. It coordinates to
Cu(1) and Cu(2) in a bis-bidentate fashion, occupying the remain-
ing equatorial [1.961(2), 1.973(2) Å] and an axial [axial 2.477(3),
2.585(3) Å] site on both centres, providing a four atom bridge
between them [Cu(1)· · ·Cu(2) 6.824 Å]. Further, the remaining cro-
conate oxygen atom coordinates to the axial site of a neighbouring
dinuclear unit, Cu(1A) [2.496(3) Å]; this bridge generates a 1D
chain structure overall. Once again the croconate bridge is almost
orthogonal [Cu(1) 81.3◦ , Cu(2) 85.5◦ ] to the equatorial planes of
the copper(II) centres, and provides a pathway for weak antifer-
romagnetic coupling (J = −9.63 cm−1 ) between the two copper(II)
centres. (H = −JS1 ·S2 ). The individual chains are linked by a weak
side-on carbonyl· · ·copper interaction [Cu(2)· · ·O(3 ) = 2.932(3) Å].
The structure of the analogous Hbpcam complex was not obtained
due to poor X-ray diffraction by the crystals, however the complex
displays much weaker antiferromagnetic coupling (J = –0.45 cm−1 )
[72]. (H = –JSA ·SB ). The authors suggest that the structural influ-
ence of the methyl groups alters the magnetic pathway and could
even have resulted in an ionic material with no covalent connection
between the [CuII (bpcam)]+ units.
An attempt to use 4,4 -bipyridine (4,4 -bipy) as the
linker produced the dimetallic complex [CuII 2 (bpca)2 (4,4 -
bipy)(H2 O)2 ](ClO4 )2 [75] in which 4,4 -bipyridine acts as a
monodentate ligand rather than a bridge. The monometallic
units are instead linked via a weak side-on interaction (2.838 Å)
between CuII and an imide oxygen atom from an adjacent unit.
Similar molecules reported in the same work were successfully
linked through 4,4 -bipyridine, highlighting the lack of predictabil-
ity when including multiple possible coordination instructions in
a supramolecular system. The thermal behaviour of the complex,
a perchlorate salt, was studied in anticipation of a phase transition
occurring, however it exploded at 339 ◦ C.
The magnetic interactions of the dithiosquarate complexes
[CuII 2 (bpca)2 (1,2-dtsq)(H2 O)]·2H2 O and [CuII 2 (bpca)2 (1,3-
dtsq)]·2H2 O have been studied and analysed using DFT calculations
[76]. Two very different magnetic pathways are possible through
the 1,2-dtsq dianion which bridges the two [CuII (bpca)]+ units
in a non-symmetric fashion (Fig. 24). The direct single atom
S(1) bridge from the axial position of Cu(1) to the equato-
rial plane of Cu(2) is responsible for ferromagnetic coupling
J = +34.2 cm−1 . There is also a four atom bridge, S(1) C C S(2),
providing another possible, but likely weak, magnetic path-
way between the equatorial positions on both Cu(1) and Cu(2)
(Fig. 24). A weak intermolecular bridge [Cu(1)· · ·S2A 3.207 Å]
propagates a weak antiferromagnetic interaction (J = –5.0 cm–1 );
H = –J(S1 ·S2 + S1a ·S2a ) – J(S1 ·S1a ). The equatorial planes of the
two imide units and the 1,2-dtsq anion are all approximately

Fig. 23. The dicopper(II) [Cu2 (bpca)2 (C5 O5 )]·3H2 O units are further connected by an interaction involving the fifth croconate oxygen atom [Cu(1a)–O(10) = 2.496(3) Å],
generating a 1D-chain complex overall. Note that hydrogen atoms and solvent molecules have been omitted for clarity.
Source: This figure was generated from data obtained from the CCDC as published originally in reference [74].
2960 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971
Fig. 24. In the structure of [CuII 2 (bpca)2 (1,2-dtsq)(H2 O)]·2H2 O two
[CuII (bpca)]+ units are bridged by 1,2-dtsq in a non-symmetric fash-
ion. Hydrogen atoms and solvent molecules have been omitted for
clarity. Cu(1)–S(1) = 2.913(1), Cu(1)–S(2) = 2.280(1), Cu(2)–S(1) = 2.324(1),
Cu(2)–O(4) = 3.241, Cu(1)–S(2a) = 3.207 Å.
Source: This figure was generated from data obtained from the CCDC as published
originally in reference [76].
orthogonal to one another [planeN1 ,N2 ,N3 , to planeN4 ,N5 ,N6 =
84.5◦ , planeN1 ,N2 ,N3 , to plane1,2−dtsq = 79.4◦ ; planeN4 ,N5 ,N6 , to
plane1,2−dtsq = 85.7◦ ].
In the complex produced using a 1,3-dtsq anion to bridge
[CuII (bpca)]+ units, the copper centres have distorted square pyra-
midal geometries and only half the complex is in the asymmetric
unit, with the other half generated by an inversion centre. The
two [CuII (bpca)]+ units are connected through all four donors of
the planar 1,3-dtsq anion. The two sulphur donors [S(1), S(1a)]
occupy the remaining equatorial site, whilst the oxygen donors
[O(3), O(3a)] occupy an axial site, on each of the copper centres
(Fig. 25) [76]. In contrast to [CuII 2 (bpca)2 (1,2-dtsq)(H2 O)]·2H2 O,
the equatorial planes of the copper(II) centres are now parallel,
but offset, due to symmetry [planeN1 ,N2 ,N3 , to planeN4 ,N5 ,N6 = 0◦ ;
offset by 4.892 Å], and are not as close to orthogonal to the dian-
ionic bridge [[planeN1 ,N2 ,N3 , to plane1,3-dtsq = 73.4◦ ]. Despite the
relatively long Cu(1)· · ·Cu(1a) separation (7.212 Å), when modelled
as a dimer of copper(II) ions the planar 1,3-dtsq anion provides
antiferromagnetic coupling of J1 = –33.6 cm−1 . A weak side-on
carbonyl-copper interaction [Cu(1)· · ·O(1b) = 2.90 Å] to an adjacent
Fig. 25. In the structure of [CuII 2 (bpca)2 (1,3-dtsq)]·2H2 O two [CuII (bpca)]+ units
are bridged by 1,3-dtsq. A weak interaction (Cu(1)· · ·O3 = 2.590 Å) has been shown
as dashed lines. Hydrogen atoms and solvent molecules have been excluded for
clarity.
Source: This figure was generated from data obtained from the CCDC as published
originally in reference [76].
Fig. 26. In the structure of [CuII 2 (bpca)2 (H2 O)2 CuII (1,2-dtcr)2 ]·2H2 O two
[CuII (bpca)(H2 O)]+ units are bridged by one [CuII (1,2-dtcr)2 ]2− . Non-acidic
hydrogen atoms and solvent molecules have been excluded for clarity.
Source: This figure was generated from data obtained from the CCDC as published
originally in reference [77].
dimetallic complex generates a loosely connected chain, so the
data can also be modelled as a magnetic chain with intramolecular
(J1 = –33.6 cm−1 ) and weaker intermolecular (J2 = –2.2 cm−1 ) anti-
ferromagnetic coupling.
The dianionic copper(II) 1,2-dithiocroconate (1,2-dtcr) com-
plex [CuII (1,2-dtcr)2 ]2− has been used to bridge two [CuII (imide)]
units, forming [CuII 2 (bpca)2 (H2 O)2 CuII (1,2-dtcr)2 ]·2H2 O (Fig. 26)
[77]. The square pyramidal copper(II) centres in the two
[CuII (bpca)(H2 O)]+ units are related by a centre of inversion. Again
the equatorial plane is occupied by the imide ligand, and in this
case a water molecule. The axial sites are bridged by a three atom,
S(2)-Cu(2)-S(2a), bridge between Cu(1) and Cu(1a) [Cu(1)· · ·Cu(1a)
8.378 Å; Cu(1)· · ·Cu(2) 4.189 Å]. The square plane of the Cu(2) centre
in the bridging dianion is almost parallel (11.4◦ ) to the equatorial
plane of Cu(1) but is considerably offset from it. No coupling was
observed between these copper(II) centres.
5.6. Chain complexes built from [Cu(imide)]+ units
In contrast to the use of dianionic linkers with [CuII (imide)]+
units, which usually produces discrete complexes as discussed in
Section 5.5 [the key exception being the 1D chain formed using cro-
conate (Fig. 23)], the use of monoanionic linkers exclusively results
in the production of polymeric chain complexes.
The chains are made up of [CuII (imide)]+ units where the imide
again provides three equatorial nitrogen donors and defines the
location of the dx2 −y2 orbital which contains the unpaired electron
density [78].
The chain complex {[CuII (bpca)](ClO4 )}∞ (tetragonal, P41 ),
revealed a previously unseen structural motif for Hbpca where the
coordination sphere of the square pyramidal metal ion is com-
prised of the N3 pocket from one imide and two imide oxygen
atoms of the imide of an adjacent complex, generating the 1D
chain (Fig. 27) [56]. Within the chain, adjacent N3 planes are almost
orthogonal to one another [88.7◦ ], the Cu· · ·Cu distance is 5.32 Å and
the bpca anion mediates a antiferromagnetic interaction of J = 10 K
[79]. (H = JS1 ·S2 ). The chains are magnetically isolated [smallest
intermolecular Cu· · ·Cu 8.07 Å]. The absence of ␲-stacking inter-
actions is somewhat surprising given the availability of aromatic
rings. The chain was crystallised from water but is not hydrated.
Nevertheless it was shown, by UV–vis studies, to dissociate into
[CuII (bpca)(H2 O)2 ]+ in aqueous solution [56].
 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971 2961

Fig. 27. The imide based chain complex {[CuII (bpca)](ClO4 )}∞ . Hydrogen atoms and uncoordinated anions have been omitted for clarity.
Source: This figure was generated from data obtained from the CCDC as published originally in reference [56].

The tricyanomethanide (tcm) anion has, in addition to the dis-
crete complexes reported in Section 5.5, been used to generate
the chain complexes [CuII (tcm)(bpca)]∞ and [CuII (tcm)(bpcam)]∞
[64,65]. The copper(II) centres of these complexes have a square
pyramidal geometry which is composed of the bpca anion and two
tcm ligands (Fig. 28). Each anionic tcm ligand acts as a 1,5-bridge
between the axial and equatorial sites on adjacent copper centres,
generating a zig-zag structural motif (Fig. 28). The equatorial-axial
nature combined with the length of the anionic tcm bridge results
in very weak antiferromagnetic coupling between the copper(II)
centres [J = −0.64 and −0.3 cm−1 for the bpca and bpcam chain
complexes, respectively] (H = − J˙ i Si · Si+1 ).
Complexes of the formula [CuII (bpca)X]∞ , where X = CN− , N3 − ,
Cl− , Br− or benzilate, form 1D chain structures [67,79,80]. These
chains are composed of square planar [CuII (bpca)X] building blocks
which are bridged through an axial site by the X of an adjacent
molecule. The axial-equatorial nature of the interaction again leads
to weak antiferromagnetic coupling between the square pyramidal
copper(II) centres, with the exception of X = CN− which shows no
interaction at all.
5.7. Copper complexes with unusual imides
Copper(II) promoted reactions have resulted in the unexpected
formation of several imide complexes, including quinoline contain-
ing [CuII (bqca)(H2 O)(OAc)] and [CuII (pqca)(H2 O)(OAc)] [22] and
2,2 -bipyridine containing [CuII 2 (bbpca)2 ](PF6 )2 (Fig. 1) [81]. The
ligands Hbqca and Hpqca have been isolated by removal of cop-
per(II) using EDTA4− (Fig. 3) [22]. In a separate study, the complex
[CuII 2 (bbpca)2 ](PF6 )2 ·EtOH·2CH3 CN resulted from hydrolysis of a
triazine complex [81]. The Hbbpca ligand has not been isolated.
The complex has a helical structure due to the unusual coordina-
tion mode of this imide ligand. Specifically, due to the presence of
a 2,2 -bipyridine moiety, this ligand is a capable of being ditopic
(Fig. 29). The result is a previously unseen binding mode, with only
two of the nitrogen donors of the N3 imide set binding to one square
pyramidal copper(II) centre, whilst the third nitrogen donor of this
set, along with the second of these two bipy donor atoms, binds to
the second square pyramidal copper(II) centre. In order to achieve
this, the imide group is twisted out of coplanarity to an uncharac-
teristically large degree: the two individual N C O planes of the
imide form an angle of 46.12◦ . The resulting helical structure is
stabilised by face-to-face ␲-stacking interactions.
5.8. Heterometallic complexes of [Cu(imide)]+ units
Discrete square tetrametallic complexes have been pro-
duced by combining [CuII (imide)]+ units with the anionic
linkers [FeIII (CN)6 ]3− [82], [FeIII (CN)3 (Tp)]− (Tp = tris(pyrazolyl)
hydroborate) [83] and [FeIII (5,5 -dmbipy)(CN)4 ]− (5,5 -
dmbipy = 5,5 -dimethylpyridine) [84].
In the two rectangular complexes [CuII 2 (bpcam)2 FeIII 2 -
(CN)6 ](PPh4 )4 ·4H2 O and [CuII 2 (bpca)2 FeIII 2 (CN)6 ](AsPh4 )4 (Fig. 30,
Table 6), by inversion symmetry the two square pyramidal
copper(II) centres and two octahedral iron(III) centres alternate
around the rectangle (one of each is present in the asymmet-
ric unit) [82]. Each [FeIII (CN)3 ]3− unit links unequally to an
equatorial and an axial site on the adjacent [CuII (imide)]+ units
via the nitrogen atoms of two cis cyanide ligands (Table 6).
Due to the axial-equatorial bridging of the [CuII (imide)]+
units, the complex [CuII 2 (bpcam)2 FeIII 2 (CN)6 ](PPh4 )4 is
modelled as a rectangle rather than a square. Hence the
magnetic interactions were modelled using the Hamiltonian
H = −J1 ·[SFe(1) ·SCu(1) + SFe(1a) ·SCu(1a) ] − J2 ·[SFe(1) ·SCu(1a) + SFe(1a) ·SCu(1) ].
This results in different strengths for the ferromagnetic coupling
between the low spin iron(III) centre and Cu(1) (J = 3.7 cm–1 )
vs Cu(1a) (J = 7.0 cm–1 ). The difference is due to the degree of
orthogonal overlap achieved along one side of the rectangle

Fig. 28. The chain complex [CuII (tcm)(bpcam)]∞ . Hydrogen atoms have been omitted for clarity.
Source: This figure was generated from data obtained from the CCDC as published originally in reference [65].
2962 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971

Fig. 29. The structure of [CuII 2 (bbpca)2 ](PF6 )2 ·2CH3 CN·CH3 CH2 OH oriented to highlight the unusual N2 /N binding mode of the imide anion and the resulting helical twist.
Hydrogen atoms, uncoordinated anions and solvents have been excluded for clarity.
Source: This figure was generated from data obtained from the CCDC as published originally in reference [81].

Table 6
The distances between copper(II) and iron(III) centres along the edges of the rectangular heterometallic complexes.

Complex Fe· · ·Cu (Å)a Fe· · ·Cu (Å)b Cu· · ·Fe· · ·Cu (◦ ) Fe· · ·Cu· · ·Fe (◦ )
II III
[Cu 2 (bpcam)2 Fe 2 (CN)6 ](PPh4 )4 4.822 4.991 77.2 102.8
[CuII 2 (bpca)2 FeIII 2 (CN)6 ](AsPh4 )4 5.041 5.211 89.9 90.1
{(Tp)2 [FeIII (CN)3 ]2 [CuII (bpca)]2 }·4H2 O 5.023 5.217 90.3 89.7
[CuII 2 (bpca)2 (H2 O)2 FeIII 2 (5,5 -dmbipy)2 (CN)8 ][CuII (bpca)FeIII (5,5 -dmbipy)(CN)4 ]·4H2 O 4.973 5.363 91.91 88.1
a
Cyanide bridge in equatorial plane of the copper centre.
b
Cyanide bridge in axial position of the copper centre.

between the magnetic (equatorial) orbital of the copper(II)
centre and the t2g magnetic orbital of the S = 1/2 iron(III)
centre. The temperature dependent magnetic properties of
[CuII 2 (bpca)2 FeIII 2 (CN)6 ](AsPh4 )4 were not reported.
The structurally similar complex {[(Tp)2 FeIII (CN)3 ]-
II
2 [Cu (bpca)]2 }·4H2 O has the same, almost square, structural
Fig. 30. In the rectangular complex [CuII 2 (bpcam)2 FeIII 2 (CN)6 ](PPh4 )4 each cop-
per(II) centre has two different CuII · · ·FeIII contacts along the edge of the rectangle.
Hydrogen atoms, uncoordinated anions and solvent molecules have been omitted
for clarity.
Source: This figure was generated from data obtained from the CCDC as published
originally in reference [82].
motif (Table 6) and hence the same arrangement of magnetic
orbitals. However, the magnetic properties were modelled with a
Hamiltonian only accounting for one exchange parameter, rather
than the two exchange parameters reported for the other exam-
ples. In this case, the analysis showed weak ferromagnetic coupling
(J = 1.38 cm−1 ; H = −2 J[SFe(1) (SCu(1) + SCu(2) ) + SFe(2) (SCu(1) + SCu(2) )]
[83]. AC measurements performed between 1.8 and 10 K showed
that the complex does not undergo magnetic ordering or slow spin
relaxation.
Ferromagnetic coupling is also observed for the co-crystallised
complex [CuII 2 (bpca)2 (H2 O)2 FeIII 2 (5,5 -dmbipy)2 (CN)8 ]-
II III 
[Cu (bpca)Fe (5,5 -dmbipy)(CN)4 ]2 ·4H2 O (Table 6). The cal-
culated coupling was smaller in the rectangular fragment
[CuII 2 (bpca)2 (H2 O)2 FeIII 2 (5,5 -dmbipy)2 (CN)8 ] (J1 = 2.64 cm−1 ;
H = −2J1 [SFe(1) ·(SCu(1) + SCu(1a) ) + SFe(1a) ·(SCu(1) + SCu(1a) )] − 2 × 2J2 SFe2
·SCu2 ), where the (CuII (bpca))+ unit is bridged both axially and
equatorially, than in the linear fragment [CuII (bpca)FeIII (5,5 -
dmbipy)(CN)4 ]2 (J2 = 5.40 cm−1 ), where the (CuII (bpca))+ unit is
linked equatorially to an iron(III) centre [84].
Repositioning of the methyl groups on the bipyri-
dine moiety led instead to the one-dimensional chain
complex {[CuII (bpca)][FeIII (4,4 -dmbipy)(CN)4 ]}∞ (Fig. 31, 4,4 -
dmbipy = 4,4 -dimethyl-pyridine) [84]. The copper(II) centres
adopt a trigonal bipyramidal geometry, with two of the three trig-
onal plane sites occupied by bridging cyanide groups, each from
a separate [FeIII (4,4 -dmbipy)(CN)4 ]− moiety, and the third site
occupied by the imide nitrogen atom. Adjacent complexes in the
chain are generated by translation, resulting in a zig-zag pattern
in which the copper(II) and low spin iron(III) centres are fer-
n−1
romagnetically coupled (J = 4.82cm−1 ; H = −J i=1 SAi · SAi+1 ).
A small intermolecular ferromagnetic coupling was also
calculated (zJ = 0.029 cm–1 ), using the van Vleck equation.
Field dependent magnetisation studies at 1.8 K revealed no
 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971 2963

Fig. 32. The structure of [CrIII (phen)(C2 O4 )2 CuII (bpca)(H2 O)]·2H2 O, a discrete
chromium(III)/copper(II) complex incorporating the [CuII (bpca)]+ unit. Hydrogen
atoms and solvent molecules have been omitted for clarity.
Source: This figure was generated from data obtained from the CCDC as published
Fig. 31. The chain complex [CuII (bpca)FeIII (4,4 -dmbipy)(CN)4 ]∞ which has both
originally in reference [86].
intra and intermolecular ferromagnetic coupling. Hydrogen atoms have been omit-
ted for clarity.
Source: This figure was generated from data obtained from the CCDC as published Ph Ph
originally in reference [84]. O O
TiCl2
O O O O
evidence for slow relaxation and hence no single chain magnet O O
behaviour. Ph Ph
+ O N
In the discrete trinuclear complex {[CuII (bpca)(H2 O)]- O N R
[AgI (CN)2 ][CuII (bpca)(H2 O)]} the two square pyrami- R
dal [CuII (bpca)(H2 O)]+ units are linked equatorially by
the NC–AgI –CN bridge. However, in the chain complex Fig. 33. A general scheme for asymmetric Diels–Alder and 1,3-dipolar cycloaddition
reactions catalysed by the chiral titanium imide complex.
{AuI [CuII (bpca)(NC)2 ]·H2 O}∞ the gold(I) ions form two types
of links, one bridging the equatorial sites and the other bridging
axial sites of the square pyramidal copper(II) ions in adjacent enantiomeric excess observed for the reactions. Elucidation of this
[CuII (bpca)(NC)2 ]− units [85]. Relatively long CuII · · ·CuII separa- intermediate structure helped the authors determine the mecha-
tions, of 15.022 Å (AgI link) and 10.085 Å (AuI equatorial-link), nism of the catalytic reaction. Similar reaction intermediates have
result. Not surprisingly, given these long separations, a magnetic been isolated by Hinterman and Seebach during a modification of
measurement of the gold(I) linked chain showed only very weak the Evans auxiliary, also used to produce chiral products [88].
antiferromagnetic coupling [J = −0.045 cm−1 ; H = −2J˙(Si · Si+1 )].
The mono-anionic linkers [CrIII (bipy)(C2 O4 )2 ]− and 6.2. Chromium
[CrIII (phen)(C2 O4 )2 ]− are in principle able to bridge [CuII (bpca)]+
units by coordination through both oxalate ligands. In prac- The complex [CrIII (bpca)2 ]ClO4 was prepared in 5.1% yield
tice, however, they instead form the discrete dimetallic by hydrolysis of TPyT (Fig. 3) [11]. Electrochemical studies in
complexes, [CrIII (bipy)(C2 O4 )2 CuII (bpca)(H2 O)]·2.5H2 O and
[CrIII (phen)(C2 O4 )2 CuII (bpca)(H2 O)]·2H2 O (Fig. 32) [86]. In both
complexes the [CuII (bpca)]+ units are connected through an axial
Cu-O bond involving a single oxygen atom of the oxalate, com-
pleting the square pyramidal coordination sphere of the copper(II)
centre, and resulting in CrIII · · ·CuII distances of 5.283 and 5.407 Å,
respectively. No magnetic interaction was observed between
the octahedral CrIII and square pyramidal CuII centres, unlike
the ferromagnetic coupling observed for the complexes where a
bis-bidentate oxalate bridges two octahedral copper(II) centres
(Section 5.5, Fig. 21).

6. Other first row transition metal ion complexes of imides

6.1. Titanium

A titanium complex containing a non-symmetric imide ligand

has been reported as the active form of a chiral alkoxytitanium cata-
lyst for Diels–Alder and 1,3-dipolar cycloaddition reactions (Fig. 33)
[87]. During the reaction the imide substrate acts as a ligand, coor-
dinating to titanium through the imide oxygen atoms (Fig. 34),
generating a chiral 6-coordinate complex and facilitating the high
Fig. 34. The structure of the imide-containing titanium chiral-catalyst intermediate.
Hydrogen atoms have been omitted for clarity.
Source: This figure was generated from data obtained from the CCDC as published
originally in reference [87].
2964 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971
Fig. 35. The structure of [MnII (bpca)2 ]·H2 O. Note that hydrogen atoms and the sol-
vent molecule have been omitted for clarity. Note that hydrogen atoms and solvent
molecules have been excluded for clarity.
Source: This figure was generated from data obtained from the CCDC as published
originally in reference [89].
acetonitrile showed reversible processes at –0.74 and –1.47 V
vs SSCE, both of which were assigned as metal based. The com-
plex was combined with iron(II) perchlorate to prepare the
chain complex {[(CrIII (bpca)2 )FeII (ClO4 )2 ]ClO4 ·CH3 NO2 ·H2 O}∞ .
The differently solvated chain complex,
{[CrIII (bpca)2 FeII (ClO4 )2 ]ClO4 ·1.5CH3 NO2 ·2.5H2 O}∞ , was pre-
pared in nitromethane by combining [CrIII (bpca)2 ]ClO4 and
iron(III) perchlorate, using catechol as an in situ reducing agent, as
purple crystals in 68% yield [11]. As for the analogous FeIII/II chains
(Section 4.2), antiferromagnetic coupling is observed between
the chromium(III) S = 3/2 and high spin iron(II) S = 2 centres
(Curie–Weiss model: CrIII /FeII  = −12.5(4) K vs FeIII/II  = −15.3(6) K
[11]), in contrast to the ferromagnetic coupling observed in the
NiII /FeII chains discussed below (Section 6.5). This is believed to be
due to both CrIII and low spin FeIII lacking electron density in the eg
orbitals, in stark contrast to NiII , which prevents propagation of fer-
romagnetic coupling with the adjacent high spin FeII ions. Whereas
both the FeIII/II and NiII /FeII chains are ferrimagnetically coupled
overall, this CrIII /FeII chain is not: the authors proposed that this
was due to the similar spin multiplicities of the chromium(III) and
high spin iron(II) centres and the weak coupling between them
[11].
6.3. Manganese
The preparation of [MnII (bpca)2 ]·H2 O (Fig. 35) was reported in
1990 [89], when it was studied for zero-field splitting parameters.
The complex was prepared as red-brown crystals by mixing Hbpca
and manganese(II) nitrate in acetone and water, using sodium
hydroxide to deprotonate Hbpca. The structure is similar to those of
other reported [MII (imide)2 ] complexes. EPR studies of the complex
and of a sample of [ZnII (bpca)2 ] doped with 1% of the complex were
performed at 130 and 298 K. These gave the axial |D| = 0.073 cm−1
and equatorial |E| = 0.017 cm−1 zero field splitting parameters. The
low A (hyperfine) value obtained is consistent with significant
unpaired electron density on the ligands.
In the discrete trinuclear complex {[MnII (bpca)2 ][MnII (hfac)2 ]2 }
the bridging [MnII (bpca)2 ] unit binds to two [MnII (hfac)2 ] moieties
via the imide oxygen atoms. As a result the Mn–Nimide (2.196 and
2.203 Å) bond distances are elongated compared to those seen
in the free [MnII (bpca)2 ] moiety (2.179 and 2.169 Å). This was
taken to suggest that the negative charge of the imide system
Fig. 36. The structure of [CoIII (bpca)2 ]ClO4 ·H2 O. Hydrogen atoms and the solvent
molecule have been omitted for clarity.
Source: This figure was generated from data obtained from the CCDC as published
originally in reference [11].
is concentrated on the imide nitrogen atom in [MnII (bpca)2 ]
but delocalises across the imide group upon coordination to the
[MnII (hfac)2 ] units. It was proposed that the increased Mn-Nimide
distances (compared to other late first row MII ) reduced the d␲–p␲
interactions between the manganese(II) and the coordinated bpca
anion, leading to the observed weak antiferromagnetic coupling
between the manganese(II) centres in the trinuclear complex
(J = –0.35 cm−1 ; H = −2J(SMn1 · SMn2 + SMn1 · SMn3 )) [90].
6.4. Cobalt
The cobalt complex [CoIII (bpca)2 ]ClO4 ·solvent (Fig. 36) was
reported in 2002 by two research groups [11,24]. In one case
[24], [CoIII (bpca)2 ]ClO4 ·CH3 OH was prepared in 70% yield by air
oxidation of the corresponding amide ligand in methanol solu-
tion with cobalt(II) perchlorate and sodium methoxide. Addition
of hydrogen peroxide increased the yield to 75%. The structure
of [CoIII (bpca)2 ]ClO4 ·CH3 OH is slightly compressed compared to
[FeIII (bpca)2 ]ClO4 , with average M–N bond lengths of 1.943 Å com-
pared to 1.978 Å.
A similar amide → imide oxidation was observed in this research
group: air oxidation of the amide complex [CoIII (L1M )2 ]BF4 was pro-
posed to have formed a mixture of the mixed amide-imide complex
[CoIII (L1M )(pypzca)]+ and the all imide complex [CoIII (pypzca)2 ]+ in
solution (Fig. 1), based on electrochemical evidence (Fig. 37) [25].
Independently of the first group, [CoIII (bpca)2 ]ClO4 ·H2 O (Fig. 36)
was also prepared by reaction of Hbpca and cobalt(II) per-
chlorate in a nitromethane/water mixture in 82% yield [11].
Electrochemical studies of the complex showed a metal based
reduction at −0.28 V vs SSCE (CoIII → CoII ) and a second reduc-
tion at −1.66 V vs SSCE. The second reduction was assigned as the
CoII → CoI reduction [11], however recent results have suggested
it may be ligand based [91]. The mononuclear [CoIII (bpca)2 ]ClO4
was then used to generate the discrete trimetallic struc-
ture {[FeII (ClO4 )2 ][CoIII (bpca)2 )2 ](ClO4 )2 (CH3 NO2 )4 } and the chain
complex {[FeII (ClO4 )2 ][CoIII (bpca)2 ]ClO4 (CH3 NO2 )(H2 O)}∞ . The
diamagnetic cobalt(III) centres separate the high spin iron(II) ions
in the chain, so the iron(II) ions are magnetically independent at
room temperature. However, between 250 and 50 K a weak fer-
romagnetic interaction of  = +0.2 (3) K was estimated using the
Curie–Weiss model.
 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971 2965

10 µA

Fig. 39. The graphite like structure of {[FeII [NiII (bpca)2 ]1.5 ](ClO4 )2 ·4.5CH3 Cl·
3CH3 OH·10H2 O}∞ . Non-coordinated anions and solvent molecules have been omit-
ted for clarity.
Source: This figure was generated from data obtained from the CCDC as published
originally in reference [10].

-1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0 tallising when water was added to the reaction solution. In
V earlier (Section 4.2), where the iron(II) centre bridges two
Fig. 37. Cyclic voltammograms of (top) [CoIII (L1E )2 ](BF4 )·0.5H2 O; (middle) fresh
[CoIII (L1M )2 ](BF4 )·0.25H2 O; and (bottom) aged [CoIII (L1M )2 ](BF4 ) that was believed
to also contain [CoIII (L1M )(pypzca)]+ and [CoIII (pypzca)2 ]+ . Scan rate: 200 mV s−1 .
Reference: 0.01 M AgNO3 /Ag.
Source: Reprinted with permission from reference [25]. Copyright 2009 Wiley.
Sodium and potassium ions have also been used to bridge
[CoIII (bpca)2 ]+ units via the imide oxygen atoms [92]. This was
achieved using a variety of co-ligands including [Co(NCS)4 ]2− ,
NCS− , N3 − and O2− . Four binding modes for the imide oxygen atoms
were observed, as shown in Fig. 38 (left to right); the common
N3 :␮-O2 mode (Fig. 2); an unusual mode where separate cations
are bound to each imide oxygen atom, providing a five atom bridge;
a mode where the imide oxygen atoms coordinate in the common
N3 :␮-O2 mode to one metal centre and another is involved in a fur-
ther (weaker) interaction; and finally another unusual mode where
the pair of imide oxygen atoms doubly bridge the two metal centres.
6.5. Nickel
The neutral building block [NiII (bpca)2 ] has also been
bridged by iron(II) centres via the imide oxygen atoms
[10,93]. In the initial study the polymeric, dark purple,
complex {[FeII [NiII (bpca)2 ]1.5 ](ClO4 )2 ·4.5CH3 Cl·3CH3 OH·10H2 O}∞
and the discrete, deep violet, trimetallic complex
{[NiII (bpca)2 ][FeII (ClO4 )2 (H2 O)2 ][NiII (bpca)2 ]·4H2 O} were pro-
duced by combining a 2:1 ratio of [NiII (bpca)2 ] and [FeII (H2 O)6 ]ClO4
in a nitromethane/chloroform mixture, the former complex
crystallising from this mixture and the latter complex crys-
comparison to the one-dimensional chain structures described
[M(imide)2 ] units, the iron(II) centre in the polymeric complex
{[FeII [NiII (bpca)2 ]1.5 ](ClO4 )2 ·4.5CH3 Cl·3CH3 OH·10H2 O}∞ bridges
three [NiII (bpca)2 ] units, resulting in a graphite-like structure
(Fig. 39). Adjacent layers are related by mirror symmetry so
are made up of all  then all  isomers of these enantiomeric
iron(II) complexes. These layers are separated by uncoordinated
perchlorate anions and solvent molecules, which also occupy
the pore spaces. Both anions and solvent can be exchanged, for
hexafluorophosphate anions and bromoform, respectively. The
discrete complex was considered to be a precursor to the polymeric
complex, and the addition of water to the reaction mixture was
used to stabilise it, allowing its isolation.
The magnetic properties of these complexes were reported
in a subsequent paper [93]. In the discrete trinuclear com-
plex, {[NiII (bpca)2 ][FeII (ClO4 )2 (H2 O)2 ][NiII (bpca)2 ]}·4H2 O,
the high spin iron(II) centre bridges two [NiII (bpca)2 ] units.
Magnetic studies revealed weak ferromagnetic coupling
between the NiII and FeII centres (J = 0.56(1) cm−1 ; H =
−2J(SNi · SFe2 + SFe2 · SNi3 )). From the structural analysis of the poly-
mer, {[FeII [NiII (bpca)2 ]1.5 ](ClO4 )2 ·4.5CH3 Cl·3CH3 OH·10H2 O}∞ , the
bond lengths indicate that the iron(II) centre is in the high
spin state (FeII –Oaverage = 2.07 Å). This is consistent with the
magnetic moment from 300 to 40 K. Below 40 K zero-field

M M
M M M M
O O O O O O O O
M
N N N N
N Co N N Co N N Co N N Co N

Fig. 38. The binding modes observed for [CoIII (bpca)2 ]+ units linked using M Na+ or K+ in the presence of various co-ligands. The first N3 :␮-O2 (Fig. 2) is common, but the
rest are unique to this study.
2966 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971

Fig. 40. The general structure of ([FeII X2 [NiII (bpca)2 ]](ClO4 )0–2 ·solvents)∞ (X = CH3 CH2 OH or CH3 CH2 CH2 OH) chain complexes where the coordinated solvents are arranged
cis around the iron(II) centre. Hydrogen atoms, uncoordinated anions and solvents have been omitted for clarity.
Source: This figure (X = CH3 CH2 OH) was generated from data obtained from the CCDC as published originally in reference [93].

splitting causes the magnetic moment to decrease signifi-
cantly. The structure of an isomorphous iron(II) chain complex
{[FeII [FeII (bpca)2 ]3 ](ClO4 )4 ·5CHCl3 ·2CH3 OH·7H2 O}∞ was also
reported, however in that case the yield and purity was limited by
the tendency of [FeII (bpca)2 ] to oxidise, so the magnetic properties
were not reported.
A series of chain complexes {[FeII X2 [NiII (bpca)2 ]](ClO4 )n ·solven-
ts}∞ where X = methanol, ethanol, 1,3-propandiol, thiocyanate and
bromide/water were also reported [93]. Despite the variation of the
charge of the complexes, due to coordination of solvent vs anions,
the structures are very similar. The key structural difference is
the arrangement of the 2 X moieties in the coordination sphere of
the iron(II) centre: cis X for ethanol (Fig. 40) and 1,3-propandiol;
trans X for the others (Fig. 41). The cis vs trans arrangements of
X result in two different orientations for the adjacent, iron(II)
bridged, imide units: either approximately orthogonal for cis
(Fig. 40) or approximately co-planar for trans (Fig. 41). Studying
the temperature dependent magnetic properties of X = methanol
and n = 2 revealed a ferromagnetic interaction between nickel(II)
and the high spin iron(II) centre with a best fit of  = +1.6(3) K,
estimated using the Curie–Weiss law.
The discrete trimetallic complexes {[NiII (bpca)2 ][MII (hfac)2 ]2 }
where MII = Mn or Fe are structurally analogous to those dis-
cussed in Sections 4.2, 5.3 and 6.3 [47]. However, in contrast
to the previous examples, weak ferromagnetic interactions
were observed between the nickel(II) (S = 1) and manganese(II)
(S = 5/2; J = +0.13(2) cm−1 ) or iron(II) (S = 2; J = 0.37(1) cm–1 ) cen-
tres, respectively (H = −2J(SM · SNi2 + SNi2 · SM )). In this family
of {[M1II (bpca)2 ][M2II (hfac)2 ]2 } complexes, the dominant spin
exchange pathway propagates through the eg orbitals of M1II .
These are occupied for M1II = Ni, and are orthogonal to the eg
orbitals on M2II : this combination gives rise to ferromagnetic
coupling.
6.6. Zinc
The diamagnetic zinc complex [ZnII (bpca)2 ]·H2 O was prepared
for use as a dopant in EPR studies of [MnII (bpca)2 ]·H2 O. However,
no physical data regarding [ZnII (bpca)2 ]·H2 O were reported [89].
7. Rhodium, rhenium and platinum complexes of imides
The first Hbpca complex of rhodium, pale yellow
[RhIII (bpca)2 ]PF6 , was synthesised in a successful attempt to
determine the hydrolysis mechanism of TPyT ligands (Fig. 3 route
(i)) [17]. The geometry of [RhIII (bpca)2 ]PF6 was described as a
distorted octahedron, with two bpca anions each coordinated
meridionally via the N3 donors. As with the first row tran-
sition metal complexes, the bond lengths to the imide nitrogen
(1.993–1.996 Å) are compressed in comparison to the pyridyl bonds
(2.015–2.048 Å). Likewise the two adjacent 5-membered chelate
rings prevent the ligand providing a 180◦ Npyridine –Rh–Npyridine
angle (intraligand: 162.7◦ and 162.9◦ ). The electrochemistry of the
complex was studied in dry dimethylformamide and the quasi-
reversible reduction of RhIII → RhI was observed as a two electron
process at −1.15 V vs Ag/AgCl. Unlike many other RhIII complexes,
perhaps due to the delocalised nature of the bpca anion, the
reduction did not resolve into two one electron processes at high
scan rates (20 V s−1 ). Irreversible reductions at −1.44 and −1.84 V
vs Ag/AgCl were assigned as ligand-based processes.
Despite the one step two electron reduction in dimethylfor-
mamide, RhIII → RhI , of [RhIII (bpca)2 ]PF6 , a later study reported
the preparation of the greenish-brown rhodium(II) complex,
[RhII (bpca)2 ]·3H2 O (Fig. 42) [94]. This was achieved by performing
hydrolysis of TPyT with rhodium(III) chloride in 1:1 ethanol:water
under an argon atmosphere, followed by washing away the ionic
[RhIII (bpca)2 ]PF6 and column chromatography of the remaining
residue which afforded the product in a yield of 20%. The mixed
ligand complex [RhII (bpca)(tpy)]Cl·8H2 O (14%) was obtained
using a similar method, starting from [RhIII (tpy)Cl3 ]. The bite
angle of the bpca anion (162.4–163.2◦ ) was similar for both
rhodium(II) complexes (Fig. 42). Results from EPR spectroscopy
of the rhodium(II) complexes showed that the unpaired electron
is located in the dx2 −y2 orbital. The complexes have an axially
compressed octahedral geometry (RhII –Nimide 1.994, RhII –Npyridine
2.040 Å), typical of [M(bpca)2 ] complexes (other than in the case of
Jahn–Teller elongated M = CuII ). The unusual stability of these low
spin (S = 1/2) rhodium(II) complexes was attributed to the absence
of an electron in the dz2 orbital significantly reducing the lability

Fig. 41. The general structure of a series of ([FeII X2 [NiII (bpca)2 ]](ClO4 )0–2 ·solvents)∞ (X = CH3 OH, NCS− and Br/H2 O) where the coordinated solvents/anions are arranged
trans around the iron(II) centre. Hydrogen atoms, uncoordinated anions and solvents have been omitted for clarity.
Source: This figure (X = CH3 OH) was generated from data obtained from the CCDC as published originally in reference [93].
 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971
Fig. 42. The crystal structure of the rhodium(II) complex, [RhII (bpca)2 ]·3H2 O.
Hydrogen atoms have been excluded for clarity.
Source: This figure was generated from data obtained from the CCDC as published
originally in references [94].
of these complexes. Electrochemical studies of [RhII (bpca)2 ]·3H2 O
in acetonitrile showed a reversible one electron process at −1.13 V
vs SCE, assigned as RhII → RhI , along with the ligand-based pro-
cesses observed for [RhIII (bpca)2 ]+ (Fig. 43). For [RhIII (bpca)2 ]PF6
a two electron reduction assigned as RhIII → RhI is observed at
approximately the same potential (Fig. 43).
The rhodium(III) complexes [RhIII (bpca)(tpy)][PF6 ]2 ·CH3 CN and
[RhIII (bpca)(2-picolinamide)Cl][PF6 ]·H2 O were also synthesised
via hydrolysis of [RhIII (tptz)Cl3 ] [95]. The crystal structure of
[RhIII (bpca)(tpy)][PF6 ]2 ·CH3 CN allowed a structural comparison of
the coordinated tridentate bpca anion and tpy ligands. The bpca
anion had a slightly smaller bite angle (80.18(9)◦ vs 81.31(9)◦ )
and remained more planar, with the exception of one imide
oxygen atom, than the tpy ligand. For the bpca anion there was
only a 3.1(2)◦ angle between the pyridyl rings whereas for tpy
the outer pyridyl rings were at angles of +4.64(2)◦ and +8.03(2)◦
relative to the central pyridyl ring. Electrochemical studies of
these complexes in dimethylformamide showed an irreversible
two electron reduction, RhIII → RhI , at –0.76 and –0.98 V vs SSCE
respectively, followed by a one electron ligand-based process at
–1.53 V vs SSCE. Along with another two rhodium(III) complexes,
solutions of [RhIII (bpca)(tpy)][PF6 ]2 ·8H2 O and [RhIII (bpca)(2-
picolinamide)Cl][PF6 ] were able to reduce carbon dioxide to
formate (determined using chromoprotic acid) under applied
Fig. 43. The cyclic voltammograms of [RhII (bpca)2 ] and [RhIII (bpca)2 ]+ in acetoni-
trile.
Source: From reference [94] – Reproduced by permission of The Royal Society of
Chemistry.
2967
Fig. 44. The cyclic voltammogram of [RhIII (bpca)(tpy)][PF6 ]2 in dry dimethylfor-
mamide when under an argon or a carbon dioxide atmosphere.
Source: Reprinted with permission from reference [95]. Copyright 1998 American
Chemical Society.
potentials of –1.44 and –1.24 V vs SSCE, respectively (Fig. 44)
[95]. Addition of small amounts of water (2.5%) to act as a
proton source significantly increased the effectiveness of these
complexes as catalysts. Under optimal conditions, at a poten-
tial of -1.49 V vs SSCE, [RhIII (bpca)(tpy)][PF6 ]2 ·CH3 CN produced
formate at a rate of 9.5 mol molcatalyst −1 h−1 with a charge effi-
ciency of 78.4%. [RhIII (bpca)(2-picolinamdie)Cl][PF6 ]·H2 O required
a smaller applied voltage (−1.31 V vs SSCE), however per-
formed at a poorer rate, 7.6 molformate molcatalyst −1 h−1 and with
a lower charge efficiency (68.4%). These rates and efficiencies
were similar to those reported for other rhodium(III) com-
plexes of bipyridyl ligands and higher than those of iridium(III)
complexes.
When the rhenium(V) amine complex [ReV 2 (␮-O)Cl2 (tris(2-
pyridylmethylamine)2 ]2+ was exposed to air for several weeks
the ligand oxidised to the imide, losing a 2-pyridylmethylamine
arm in the process, to form the imide complex [ReIII 2 (␮-
O)O2 Cl2 (bpca)2 ]·CH3 CN (Fig. 45) [96]. This was the first example of
an O = ReIII –O–ReIII O bridge in a complex with a tridentate ligand.
No further properties of the complex were discussed.
Fig. 45. The crystal structure of [Re2 (␮-O)O2 Cl2 (bpca)2 ]·CH3 CN. Hydrogen atoms
and uncoordinated solvent molecules have been omitted for clarity.
Source: This figure was generated from data obtained from the CCDC as published
originally in reference [96].
2968 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971
Fig. 46. Coordination sphere around the europium ion (left) within the structure of the [EuIII 3 (bcpca)3 (H2 O)6 ]·3DMSO·12H2 O complex (right). Non-acidic hydrogen atoms
and uncoordinated solvent molecules have been omitted for clarity.
Source: This figure was generated from data obtained from the CCDC as published originally in reference [13].
8. Lanthanide complexes of imides
8.1. Overview of lanthanide complexes
The incorporation of lanthanide (Ln) ions opens up many fur-
ther possibilities, including the study of luminescence [97] and of
magnetic properties resulting from 3d–4f interactions [41]. Three
classes of imide lanthanide complexes have been reported, those
in which the lanthanide ion: (a) is bound in the N3 pocket, (b)
is bound by the ␮-O2 of a transition metal [M(imide)2 ]0/+ com-
plex, (c) is co-crystallised with a transition metal [M(imide)2 ]0/+
complex. These three classes are presented and discussed in the
following three sections. In the first of these, the basic design of
Hbpca has been adapted to produce pentadentate imide ligands
(Fig. 1) capable of binding the lanthanide ions, which prefer higher
coordination numbers and carboxylate donors (Section 8.2). The co-
crystallised systems are described for completeness (Section 8.3).
Transition metal imide complexes have also proven effective for
bridging lanthanide ions through the imide oxygen atoms (Section
8.4; Fig. 2, N3 :␮O2 ). These distinct structural outcomes appear to
depend on both the choice of co-ligands and the charge of the imide
complex.
8.2. Lanthanide complexes of imide ligands
The ligand bis(6-carboxypyridine-2-carbonyl)amine (H3 bcpca,
Fig. 1) has been used to produce the only examples of an imide
binding to a lanthanide through the N3 donor set (Fig. 2) [13,14].
The methyl ester of H3 bcpca hydrolyses by the combination of
coordination to the Lewis acidic lanthanide ion and the pres-
ence of 3.6 equivalents of sodium hydride, in DMF, producing the
triangular complexes [EuIII 3 (bcpca)3 (H2 O)6 ]·3DMSO·12H2 O and
[GdIII 3 (bcpca)3 (H2 O)6 ]·3.5DMSO·12H2 O (Fig. 46), after recrystalli-
sation by water diffusion into a DMSO solution. One third of the
triangle, a [LnIII (bcpca)(H2 O)2 ] moiety, is present in the asymmet-
ric unit, with the other two thirds of the triangle generated by a
three-fold axis. The imide ligand has a pentadentate pocket made
up of the usual N3 donor set plus two oxygen atoms from the
pendant carboxylate groups. The coordination sphere of the lan-
thanide ion is completed by one coordinated water molecule sited
below the N3 plane of the bcpca anion, and a coordinated water
molecule and a pair of bridging imide oxygen atoms from an adjacent
[LnIII (bcpca)(H2 O)2 ] unit, both of which sit above this plane. The
lanthanide ion itself sits 0.855 (Eu) and 0.846 (Gd) Å above this N3
plane. The coordination of the pair of bridging imide oxygen atoms
from the adjacent complex is complimentary, such that the crystal-
lographic three-fold axis generates a triangle of these units (Fig. 46).
Comparison of the solid state and solution luminescence spectra
of [EuIII 3 (bcpca)3 (H2 O)6 ] led to the conclusion that the triangular
structure was maintained in solution. The expected series of 5 D0 →
7 F transitions was observed, with an overall quantum yield of 37%.
x
Both complexes were evaluated [14] for potential use as medical
magnetic resonance imaging (MRI) agents [98]. Magnetic stud-
ies of the [GdIII 3 (bcpca)3 (H2 O)6 ]·3.5DSMO·12H2 O triangle complex
showed that no interaction occurred between the GdIII (S = 7/2)
centres [14]. The molecular relaxivity of the complex was studied
by NMR spectroscopy on a 9:1 water/dimethylformamide solu-
tion and was calculated to be 28.5 s−1 mM−1 at 20 MHz, with a
density of relaxivity of 18.8 g mol–1 s–1 mM–1 , a reasonably good
value. The relaxivity of the complex was limited by the rela-
tively slow exchange rate of the coordinated water molecules
(0.3 × 106 s−1 ). As part of the study, the thermodynamic stability
of [EuII 3 (bcpca)3 (H2 O)6 ] was also evaluated from a titration with
EDTA4− . The results showed that, whilst not stable enough for med-
ical applications [98], the complexes were reasonably stable at a
range of physiological pH values and in the presence of competing
ligands [14].
8.3. Co-crystallisation of transition metal imide complexes with
lanthanide ions
Mononuclear imide complexes such as low spin [FeIII (bpca)2 ]+
could reasonably be expected to coordinate to lanthanide
ions through the imide oxygen atoms. While this is pos-
sible (Section 8.4), there have also been reports of co-
crystallisation products, namely [FeIII (bpca)2 ][EuIII (NO3 )4 (H2 O)2 ]
[99] and [FeIII (bpca)2 ][ErIII (NO3 )3 (H2 O)4 ]NO3 [100]. In these com-
plexes only weak hydrogen bonds connect the discrete transition
metal and lanthanide complexes. Magnetically the d and f electron
systems of the discrete complexes do not interact and the imide
units act to physically and magnetically isolate the lanthanide ions.
Magnetic studies and ab intio calculations were used to determine
and model the easy axis of magnetisation of the lanthanide ions.
 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971
Fig. 47. The crystal structure of [FeIII (bpca)(␮-bpca)DyIII (NO3 )4 ]·H2 O·4.5CH3 NO2 .
Hydrogen atoms, uncoordinated anions and solvent molecules have been omitted
for clarity.
Source: This figure was generated from data obtained from the CCDC as published
originally in reference [9].
8.4. Lanthanide complexes of transition metal/imide
metalloligands
In the dinuclear 3d–4f complex [FeIII (bpca)(␮-
bpca)DyIII (NO3 )4 ]·H2 O·4.5CH3 NO2 , prepared in a imide oxygen atoms resulting in cancellation of the Ising anisotropy
methanol/nitromethane mixture, the N3 :␮-O2 binding mode
(Fig. 2) occurs with the low spin [FeIII (bpca)2 ]+ cation coordinated
to the dysprosium(III) ion via both of the imide oxygen atoms
(Fig. 47) [9]. The remainder of the 10-coordinate dysprosium(III)
coordination sphere is completed by four bidentate nitrate anions.
Unlike the series of transition metal complexes discussed above,
the [Fe(bpca)2 ]+ only coordinates through one of the two sets of
imide oxygen atoms available, resulting in a dinuclear, rather than
a trinuclear or polymeric, complex. Magnetisation measurements
between 0.4 and 4.2 K showed hysteresis loops and steps in the
magnetisation. AC susceptibility measurements showed slow
relaxation of magnetisation consistent with SMM behaviour. An
ab-initio study of the ligand field, spin-orbit and exchange effects
of the 3d–4f system was used to model the 3d–4f interaction
Fig. 48. The structure of the discrete trimetallic complex [(DyIII (hfac)3 }2 )(FeII (bpca)2 )]·CHCl3 . Hydrogen atoms and uncoordinated solvent molecules have been omitted for
clarity.
Source: This figure was generated from data obtained from the CCDC as published originally in reference [101].
2969
(FeIII S = 1/2, DyIII S = 5/2), which occurs via the  skeleton of the
ligand rather than the delocalised system.
The neutral imide building blocks [NiII (bpca)2 ] and [FeII (bpca)2 ]
have been used as bridging moieties to generate the isostructural
discrete trinuclear species {[DyIII (hfac)3 ]2 [MII (bpca)2 ]}·CHCl3 with
MII = Ni or Fe (Fig. 48), similar to those seen in previous Sections 4.2,
5.3, 6.3 and 6.5 but with an additional hfac ion bound per Ln, from
a chloroform solution [101]. Unlike in the above dinuclear complex
[FeIII (bpca)(␮-bpca)DyIII (NO3 )4 ] (Fig. 47), in these two cases the
imide complex bridges two eight-coordinate lanthanide ions, using
both sets of imide oxygen atoms to do so. This raises the question of
whether the nature of the co-ligands on the lanthanide ion or, more
intuitively, the charge on the central imide unit, is responsible for
the difference in terminal vs bridging coordination by the imide
complex. Further examples are required before this point can be
confidently addressed.
Within these trinuclear complexes the Dy· · ·Dy separations are
11.31 (M = NiII ) and 11.46 Å (M = FeII ). Although no weak interac-
tions are observed between the discrete trinuclear complexes, the
shortest Dy· · ·Dy separations are actually intermolecular (NiII 9.84,
FeII 9.53 Å). These two complexes provide an excellent case study to
investigate how the orbital pathways provided by the nickel(II) vs
iron(II) bridges affect communication between the two lanthanide
ions. In contrast to the diamagnetic iron(II) bridge, the paramag-
netic nickel(II) bridge (S = 1), with occupied eg orbitals, provides
a pathway for ferromagnetic coupling between the two dyspro-
sium ions (each S = 5/2). Surprisingly, this ferromagnetic interaction
halved the activation barrier required for reversal of magnetisa-
tion. This was ascribed to the orthogonal orientation of the bridging
between the two individual dysprosium(III) ions.
The neutral imide building block [NiII (bpca)2 ] has also been used
to bridge lanthanide ions through both sets of imide oxygen atoms
to produce three 1-dimensional chain complexes with the formula
{[LnIII (NO3 )(H2 O)3 ][NiII (bpca)2 )](NO3 )2 ·3H2 O}∞ where LnIII = Gd,
Tb or Dy, from a dichloromethane/ethanol solution (Fig. 49) [102].
Here the nine-coordinate lanthanide ion binds four imide oxy-
gen atoms, three water molecules and one bidentate nitrate anion.
Hence, unlike the previous examples where all of the nitrate anions
are coordinated, this structure has two uncoordinated nitrate
anions per repeating unit. Unlike the discrete systems, which have
no uncoordinated anions, there are several intermolecular inter-
actions between the chains that are mediated by the numerous
uncoordinated anions present. These include a significant hydrogen
2970 M.G. Cowan, S. Brooker / Coordination Chemistry Reviews 256 (2012) 2944–2971
Fig. 49. The LnII Gd example of the isostructural series {[LnIII (NO3 )(H2 O)3 ][NiII (bpca)2 )](NO3 )2 ·3H2 O}∞ . Hydrogen atoms and uncoordinated solvent molecules have been
omitted for clarity.
Source: This figure was generated from data obtained from the CCDC as published originally in reference [102].
bonding network involving both coordinated and uncoordinated
anions and solvent molecules. Further intermolecular connections
between adjacent chains occur via stacking interactions between
pyridyl rings. Despite the observation of ferromagnetic exchange
within the chain, the numerous intermolecular interactions pre-
cluded the observation of SCM behaviour.
Interestingly, in the similar chain complexes
{[(LnIII (NO3 )3 ][MII (bpca)2 ]·xH2 O}∞ (LnIII = Gd, Tb, Dy, Ho, Y(Ni
II
only) and M = Ni, Zn) all of the nitrate counter-ions are coordinated
to the ten-coordinate lanthanide centres, the only difference in
preparation being the use of methanol/chloroform as the solvent
[103]. For this system, no intermolecular interactions are reported
between the chains. Consequently the chains are magnetically
isolated, and the three chains where MII = Ni and LnIII = Tb, Dy or Ho
exhibit slow relaxation of magnetisation in a DC field at tempera-
tures between 1.8 and 10 K (field induced single molecule magnet
behaviour). Where the lanthanide ions are separated by diamag-
netic [ZnII (bpca)2 ] bridges, the magnetic properties are similar to
those of isolated Ln(III) ions. Nevertheless these zinc/lanthanide
complexes also undergo slow relaxation when a DC field is applied
(field induced single molecule magnet behaviour).
9. Concluding remarks
The synthesis, structure and properties of the twelve imide lig-
ands and over 150 structurally characterised imide complexes of
those ligands reported before June 2011 have been reviewed. The
imide ligands are most commonly observed to bind through an N3
donor set which includes the deprotonated imide nitrogen atom,
but are also observed to form bonds through the pair of imide oxy-
gen atoms, and sometimes via both. Other binding modes have also
been observed on rare occasions, so overall imide ligands are clearly
established as an extremely versatile ligand type.
Both discrete and polymeric, homometallic and heterometallic,
complexes have been produced and the influence of weak inter-
actions and inclusion of simple co-ligands has produced a wide
variety of structures. To date, studies of these materials have pre-
dominantly focussed on the investigation of magnetic properties,
with particular highlights being the observation of single molecule
and single chain magnetism. Other useful properties observed for
these complexes include reversible redox processes and the elec-
trocatalytic reduction of carbon dioxide; (gradual) spin crossover;
luminescence; anion and solvent exchange; and semi-conductor
behaviour. Given the wealth of properties reported to date, despite
the very limited number of imide ligands employed and the
limited exploration of metal ions other than iron and copper, there
is clearly plenty of scope for further development. Indeed it is clear
from this review that considerable potential exists for the design,
development and investigation of new generations of imide based
ligands and coordination complexes with exciting properties. Such
studies are currently underway in many of the groups referenced
above, as well as in this group [91,104], and in others [105].
Acknowledgements
We are grateful to the University of Otago for funding this
research (including the award of a Postgraduate Scholarship to
MGC) and to Dr David McMorran (University of Otago) for proof-
reading an early version of this review.
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