Coordination Chemistry Reviews 303 (2015) 1–31

Contents lists available at ScienceDirect

Coordination Chemistry Reviews

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

Review

Recent advances in acylpyrazolone metal complexes and their

potential applications
Fabio Marchetti a,∗ , Riccardo Pettinari b , Claudio Pettinari b
a
School of Science and Technology, University of Camerino, Chemistry Section, Via S. Agostino 1, 62032 Camerino, MC, Italy
b
School of Pharmacy, University of Camerino, Chemistry Section, Via S. Agostino 1, 62032 Camerino, MC, Italy

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Ligands synthesis, structure and substituents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Ligands biological properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
4. Metal complexes of acylpyrazolones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4.1. Group 1: Na and K . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4.2. Group 2: Mg, Ca, Sr and Ba . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4.3. Group 3: Sc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4.4. Group 4: Ti, Zr and Hf . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4.5. Group 5: V . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.6. Group 6: Cr, Mo and W . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.7. Group 7: Mn . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.8. Group 8: Fe and Ru . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.9. Group 9: Co, Rh and Ir . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.10. Group 10: Ni, Pd and Pt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.11. Group 11: Cu and Ag . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4.12. Group 12: Zn . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.13. Group 13: B and Al . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.14. Group 14: Sn and Pb . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4.15. Lanthanides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.16. Actinides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
5. Conclusion and perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29

Abbreviations: Me, methyl; Et, ethyl; Pr, propyl; iPr, iso-propyl; Bu, butyl; tBu, tert-butyl; Pe, pentyl; nPe, neopentyl; He, hexyl; Cp, cyclopentyl; EtCp, ethyl-
cyclopentane; Cy, cyclohexyl; Ph, phenyl; Bn, benzyl; Biph, biphenyl; F5Ph, pentafluorophenyl; CHPh2, diphenylmethyl; Pd, pentadecyl; Hd, heptadecyl; 1naph,
1-naphthyl; 2naph, 2-naphthyl; py, pyridin-2-yl; pyCOOH, 6-carboxylic acid-2-pyridinyl; fur, 2-furyl; thi, 2-thienyl; norb, 5-bicyclo[2.2.1]hept-5-en-2-yl; AD, adamantyl;
Ph2OH, 2-hydroxyphenyl; Ph4F, 4-fluorophenyl; Ph4Cl, 4-chlorophenyl; Ph3Cl, 3-chlorophenyl; Ph4Br, 4-bromophenyl; Ph4I, 4-iodophenyl; Ph4Me, 4-methylphenyl;
Ph4NMe2, 4-dimethylaminophenyl; Ph4CN, 4-cyanophenyl; CF3, trifluoromethyl; Ph4CF3, 4-trifluoromethylphenyl; CF2CF3, pentafluoroethyl; Ph4tBu, 4-tert-butylphenyl;
Ph4NO2, 4-nitrophenyl; dme, 1,2-dimethoxyethane; thf, tetrahydrofurane; dmf, dimethylformamide; OAc, acetate; tetraglyme, 2,5,8,11,14-pentaoxapentadecane;
tmeda, N,N,N ,N -tetramethylethylenediamine; pmdien, N,N,N ,N ,N -pentamethyldiethylenetriamine; Cp*, pentamethylcyclopentadienyl; phen, 1,10-phenanthroline;
bipy, 2,2 -bipyridine; tpq, 2-(thiophen-2-yl)quinolone; ppy, 2-phenylpyridine; dbzm, dibenzoylmethane; dfppy, (2,4-difluoro)phenylpyridine; dmso, dimethylsulphox-
ide; dpephos, bis[2-(diphenylphosphino)-pheny]ether; saph, salicylidene-o-aminophenol; DCJTB, 4-(dicyanomethylene)-2-tertbutyl-6(1,1,7,7,-tetramethyljulolidyl-9-
enyl)-4H-pyran; aac, N-phthaloyl aminoacids; acac, acetylacetone; bzac, benzoylacetone; TPPO, triphenylphosphine; dppmO2 , bis(diphenylphosphino)methane
oxide; dppeO2 , bis(diphenylphosphino)ethane oxide; dpppO2 , bis(diphenylphosphino)propane oxide; dppbO2 , bis(diphenylphosphino)butane oxide; pyphenCN,
pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile; 4,4 -Me2 bipy, 4,4 -dimethyl-2,20-bipyridyne; DPPOC, 9-(4-tert-butylphenyl)-3,6-bis(diphenylphosphineoxide)-
carbazole; batophen, 4,7-diphenyl-1,10-phenanthroline; DB18C6, dibenzo-18-crown-6; DEDPU, N,N -diethyl-N,N -diphenylurea; DPDPU, N,N -dipropyl-N,N -diphenylurea;
DBSOB, 1,4-di(butylsulfinyl)butane.
∗ Corresponding author. Tel.: +39 0737 402217; fax: +39 0737 637345.
E-mail address: fabio.marchetti@unicam.it (F. Marchetti).

http://dx.doi.org/10.1016/j.ccr.2015.05.003
0010-8545/© 2015 Elsevier B.V. All rights reserved.
2 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31
a r t i c l e i n f o a b s t r a c t
Article history: This review is aimed at updating the current advance of metal complexes bearing acylpyrazolonate lig-
Received 6 March 2015 ands. Novel synthetic procedures for acylpyrazolones are reported together with a survey of the ligands
Accepted 10 May 2015 biological properties. All the literature since 2005 on metal complexes (main group, transition, lanthanide
Available online 18 May 2015
and actinide metals) containing acylpyrazolones is reported together with a discussion on their main
structural features and field of potential applications.
Keywords:
Acylpyrazolone ligands
Metal complexes
Coordination chemistry
1. Introduction
␤-Diketones and related ligands have attracted the interest of
researchers since the dawn of coordination chemistry, with the
preparation of acetylacetone first described by Claisen more than
100 years ago [1], and continue to be used as ligands of choice for
the synthesis of metal complexes that find application in a number
of fields [2]. Much efforts have been devoted to the prepara-
tion and characterization of functionalized ␤-diketones suitable to
finely modulate the physico-chemical features of the correspond-
ing metal complexes, for example volatility and thermal stability
sufficient to employ them as molecular precursors in chemical
vapour deposition (CVD) techniques, or luminescence in view of
potential application in the fabrication of polymer light-emitting
diodes for low-cost, full-color, flat-panel displays, or even mag-
netic and electronic properties of metal ␤-diketonates as liquid
crystal phases. But transition- and lanthanide-metal derivatives
also display interesting catalytic features, where the ␤-diketonates
are important spectator donors for metal-intermediate species
involved in a number of organic reactions, and find increasing inter-
est as supramolecular assemblies in material chemistry.
Besides classical ␤-diketones, an interesting functionalization
has been the fusion of a pyrazole ring to the chelating arm, affording
a novel family of enolizable ligands, named 4-acyl-5-pyrazolones,
the first synthesis of such molecules being reported at the end
of the XIX century [3], even if only in 1959 Jensen published
an advantageous method of preparation of 1-phenyl-3-methyl-4-
acylpyrazol-5-ones [4]. These ligands have been used for a long
time as convenient metal extractants or chelating reagents in the
spectroscopic determination of metals in traces, largely used in ana-
lytical chemistry for determination and isolation of almost all metal
ions, due to high extracting ability of acylpyrazolonates, lower pKa
values in comparison with conventional ␤-dicarbonyl compounds,
great separation power, intense color of the complex extracts and
low-solubility of the complexes in some solvents [5]. The inter-
esting feature of this family of molecules with respect to classical
␤-diketones, stemming in the presence of the pyrazole ring, is also
related to the evidence that ccompounds containing pyrazole func-
tionality exhibit anti-inflammatory and analgesic activity [6].
In 2005 we reviewed the most important synthetic routes of this
family of ligands and their coordination chemistry toward many
metal ions, from main group to transition, lanthanide and actinide
metals and relevant applications of their metal complexes [7]. After
ten years we have decided to update the knowledge in this field,
because many other papers have appeared in the last decade, deal-
ing on acylpyrazolone ligands and their metal complexes, with
novel potential applications and future perspectives.
2. Ligands synthesis, structure and substituents
Following previous review [7], we will limit the discussion on
the coordination chemistry of 1-R1 -3-R2 -4-R3 (C O)-pyrazol-5-one
proligands (Fig. 1), here indicated as HQ in general, where H is an
enolizable proton.
© 2015 Elsevier B.V. All rights reserved.
There exist many variations in this class of molecules, regarding
mainly the donor atoms in the chelating ring, i.e. a sulphur or a
nitrogen atom at the place of one or both oxygen atoms of chain and
pyrazole carbonyls, and they have been reviewed by Casas some
years ago [8]. Here we will use the same symbolism previously
proposed: symbols up to right of Q indicate the substituents R1 ,
R2 and R3 . However, generally R1 = Ph, R2 = Me, so that in this case
only R3 will be indicated, i.e. HQtBu means R1 = Ph, R2 = Me, R3 = tBu
(Fig. 2a). By contrast, when R1 = / Ph, R2 = Me, both R1 and R3 will
be indicated up to right of Q, i.e. HQMe,Ph means R1 = Me, R2 = Me,
R3 = Ph (Fig. 2b). Finally, only when R1 =
/ Ph and R2 =/ Me, all R1 , R2 ,
R3 groups will be indicated, i.e. HQMe,Ph,Me means R1 = Me, R2 = Ph,
R3 = Me (Fig. 2c).
The tautomerism of 4-acylpyrazolones (Fig. 3) has been the
subject of various studies: in solution a fast (relative to the NMR
timescale) interconversion of OH and NH forms gives rise to aver-
aged sets of signals [9]. The chelated hydroxy forms A, B, E and F
are predominant in CDCl3 or C6 D6 , and mixtures of OH and NH tau-
tomers are present in the more-polar [D6 ]DMSO. In the solid state,
some unambiguous results have been obtained by single-crystal X-
ray studies showing HQ proligands, crystallized from chloroform,
in the enol form B [10], while the amino diketonic form C, stabilized
by an extensive network of intermolecular N H· · ·O bonding, was
confirmed from re-crystallization in polar solvents like methanol
[10a,b,11]. 13 C and 15 N CPMAS spectra suggest the zwitterionic
structure H for HQpy,CF3 (Fig. 3) [12].
The synthesis of HQ is based on direct acylation of 5-pyrazolones
with acyl chlorides or anhydrides in the presence of calcium
hydroxide in dioxane or thf at reflux [4]. Subsequent treatment with
acid aqueous solution affords the HQ in high yield as a solid powder
generally insoluble in water, apart few examples such as HQMe,Me ,
which displays a quite good solubility in water and must be iso-
lated by extraction with dichloromethane [7]. Concerning the use
of calcium hydroxide, Kurteva have proved that calcium hydroxide
R3
2
R O
3 4
N2 1
5
OH
N
R1
Fig. 1. Generic structure for acylpyrazolones.
R3 R3 R3
Me O Me O R2 O
N OH N OH N OH
N N N
1 1
Ph R R
HQ R3
HQ R1,R3
HQR1,R2,R3
Fig. 2. Symbolism used in this review for the acylpyrazolones.
 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31 3

R3 R3 R3 R3 H
Me H Me Me H Me
O Me O Me O Me O O

N N H N N N OH N N
N OH N O H N O N O N N N
OH O
R1 R1 R1 R1

A B C D

HQH self-condensation product

R3 R3 HO
Me OH Me O Me
H N
N O N O N O
N N N
R1 R1 R1
E F G H
Fig. 3. Tautomeric forms of acylpyrazolones.
does not “catalyze” the reaction, as claimed in the original work
of Jensen, instead it is used to push the tautomeric equilibrium
toward the enol form, to protect the hydroxyl functionality as a
complex, to trap the liberated hydrogen chloride, and to keep the
reaction media basic [13]. In fact, C-acylation at the fourth position
of pyrazolone can be achieved only if the starting pyrazolone is in
the enol form and the OH group is protected to avoid O-acylation.
Calcium hydroxide is able to play the dual role to afford the required
pH needed to form the enol and also to coordinated the hydroxyl
functionality. Additionally, the excess of Ca(OH)2 (at least 2 equiv
with respect to acyl chloride) is necessary to trap the liberated
hydrogen chloride, and thus keep the media basic, so that avoiding
decomposition of the complex during the acylation step.
An improvement in the synthesis of specific acylpyrazolones
containing a pyridine ring in R1 position, firstly synthesized and
used by us in 2004 [14], has been recently reported by Bian, who
have used calcium and barium hydroxide in 1:4 ratio as basic
agents in dioxane, at the place of pyridine, to prepare a number
of 1-(pyridin-2-yl)-3-methyl-4-aroyl-5-pyrazolones (Fig. 4) [15].
Bochkarev also used Ba(OH)2 in conjunction with Ca(OH)2 for the
synthesis of HQnorb (1-phenyl-3-methyl-4-(5-bicyclo[2.2.1]hept-
5-en-2-yl)-5-pyrazolone) containing a norbornene functionality in
the acyl moiety (Fig. 4) [10g].
Another synthetic protocol is related to the preparation of 1-
phenyl-3-methyl-4-formyl-2-pyrazolin-5-one HQH , where R3 is
simply an hydrogen (Fig. 5). The synthesis of 5-oxo-2-pyrazoline-
4-carboxaldehydes was reported in 1961 [16], by the condensation
of 1-phenyl-3-methyl-2-pyrazolin-5-one with POCl3 in DMF, but
purification and characterization of these molecules was difficult,
due to tendency to self-condense affording the species shown in
R3
Me O Fig. 5. Structures of HQH and of its self-condensation product.
R3
N O
Fig. 5. Only in 2008 the proligand HQH has been re-synthesized and
H used as chelating agent toward the vanadyl ion [17].
N
Poly(arylether) dendritic HQGn (n = 0–3) (Fig. 6), based on the
4-phenylacetyl-5-pyrazolone group were synthesized by intro-
ducing Fréchet-type dendritic branches [18]. As no product was
obtained by the condensation of the dendritic ␤-diketone esters
with hydrazine at room temperature, it was necessary to increase
the reaction temperature and prolong the reaction time; the pyra-
zolone dendrons were obtained in refluxing xylene under inert N2
atmosphere in 2 days.
A potentially tridentate 4-(2-hydroxybenzoyl)-2-(pyridin-2-
yl)-1H-pyrazol-3-ol proligand H2 Qpy,Ph2OH , containing both a
pyridine ring in R1 and a orto-hydroxyphenyl group in R3 (Fig. 7),
has been prepared from 3-acetyl-4-hydroxycoumarin and 2-
hydrazinopyridine in a 1:1 molar ratio in refluxing methanol [19].
3. Ligands biological properties
We consider useful to report here also a survey on the bio-
logical properties of acylpyrazolones, as they strictly resemble
a well-known family of molecules, antipyrine (also known as
phenazone, 2,3-dimethyl-1-phenyl-5-pyrazolone) (Fig. 8) and its
derivatives, that exhibit a wide range of biological activities and
applications [20]. Antipyrine is a marker in the study of transfer
and bio-transformations of drugs in the human body [21] and its
metabolites show a positive correlation with plasma fibronectin
level in monitoring patients with chronic liver illness (HBV, HCV
and alcohol-related disease) [22]. Antipyrine is analog to edaravone
(3-methyl-1-phenyl-5-pyrazolone) (Fig. 8), which represents the
most important precursor in the synthesis of many acylpyra-
zolones. Edaravone also displays important biological features: it
has been used for brain disorders [23] and myocardial ischemia
[24], moreover it displays antipyretic and analgesic activity [25].
Analogs of edaravone are known as anticancer drugs since 1966
[26].
Several paper appeared on the biological properties of
acylpyrazolones, ranging from anti-inflammatory to antiprion and
also antimicrobial agents. A number of rigid acylpyrazolones

R3
Me O Me O
R3 = F
N OH N OH
N N

HQ py,R3 HQnorb

Fig. 4. Novel 1-(pyridin-2-yl)-3-methyl-4-aroyl-5-pyrazolones HQpy,R3 and the proligand HQnorb .

4 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31

O O O N N
CO(OEt)2 PhNHNH2
Gn Gn OEt Gn
NaH/thf Xylene O
PhCH2COCl
Ba(HO)2, Ca(OH)2

N N O N N
N N
O O
Gn
O O O
O
O

HQG0 HQG1
D

D
O O

D O
O O
O N N
O
O O O N N
D O
O O O
D O
O O O
O
HQG2

D O
O HQG3
O
O
D= D

O
O
D

Fig. 6. Synthetic procedure for dendritic HQGn proligands (n = 0–3).

O O OH O OH
O O
HN
O HN N N N
N
NH2 N
OH OH Me

H2Qpy,Ph2OH

Fig. 7. Synthetic route to H2 Qpy,Ph2OH .

HQ4RPh,Ph4Cl (Fig. 9) have shown high activity against Mycobac- Several acylpyrazolones and their metal complexes display an
terium tuberculosis (MTB), the causative agent of tuberculosis, and inhibitory effect on TNF-␣ induced expression of ICAM-1 (inter-
a computational analysis indicates the fundamental role of the p- cellular adhesion molecule-1, which plays a critical role in the
chlorophenyl moiety at C4 in the antimycobacterial activity [27]. immune responses and inflammation) on human endothelial cells
[28]. Since acylpyrazolones can exist in several tautomeric forms,
Me Me those corresponding to HQPh were investigated using density func-
tional theory, and docking of all HQPh tautomers on ICAM-1 protein
N O N O indicates one keto-enol form favored to act in biological environ-
Me N N
ment.
Some acylpyrazolones show a potent activity of inhibiting
protease-resistant prion protein accumulation. Among them, the
HQPh displays the highest activity against ScN2a cells [29]. The
proligands HQCF3 and H2 Q8Q (Fig. 10) possess anti-inflammatory
Antipyrine Edaravone
properties in vivo by intra-peritoneal administration to rats, signif-
Fig. 8. Structures of antipyrine and edaravone. icantly reducing carrageenan induced inflammation [30].
 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31 5

Cl Me Me
Me
Me Me
Me
Me O
Me O Me O
N OH
N N N
N OH OH
N
R = H, F, Cl, Br, Me

R
HQnPe HQPh4tBu
HQ4RPh,Ph4Cl
Fig. 11. Structure of proligands HQnPe and HQPh4tBu .
Fig. 9. Structure of proligands HQ4RPh,Ph4Cl .

4. Metal complexes of acylpyrazolones

Acylpyrazolones are iron chelators with high affinity for ferric By treatment with a base such as NR3 , or KOH, or NaOMe, the
ions and different affinity for ferrous ions, so they could be bene- HQ ligands can be deprotonated and display several coordination
ficial in different pathologies, as in the treatment of iron excess in modes, which have been exhaustively reported in the previous
overtransfused patients or in hereditary iron overload diseases and review [7]. Here we cover the literature on metal complexes of
in acute iron intoxications [31]. None of the tested acylpyrazolones acylpyrazolones from 2005.
was able to reduce ferric ions and most of them were powerful
inhibitors of Fenton chemistry.
A long-chain HQHe (1-phenyl-3-methyl-4-heptanoyl-5- 4.1. Group 1: Na and K
pyrazolone) shows limited inhibitory activity in vitro against
some human pathogenic bacteria (Bacillus subtilis, Escherichia coli, The compound Na(QPh ) shows inhibitory activity toward ICAM-
Staphylococcus epidermidis, and Staphylococcus aureus) [32]. HQH 1, lower than the proligand HQPh [28]. The complex Na(QiPr )(dme)
is active against S. aureus, E. coli, and Pseudomonas aeruginosa [17]. is a 1D coordination polymer [Na(QiPr )(dme)]n , where the main
The acylpyrazolones HQPh4F , HQPh4Cl , HQPh4Br are active against repeating unit of the 1D chain is a centrosymmetric dimeric
S. aureus, Streptococcus viridans, E. coli, Fusarium oxysporum, fragment {Na(QiPr )(dme)}2 containing QiPr ligands acting as both
Alternaria alternata, and Alternaria solani, while HQCF3 is essentially O,O -chelating toward a Na atom and bridging through the pyra-
inactive against all strains [33]. zolone oxygen to a second Na atom (Fig. 12) [37].
The proligands HQMe and HQPh display fungicidal and A potassium coordination polymer [K2 (QPh )2 (H2 O)3 ]n ·2nH2 O is
insecticidal activities against Trichoderma viridae (soil fungus), Col- based on adjacent chains lying parallel to each other and con-
letotrichum gloeospoioides (banana fungus), Verticillium fungicola nected by water molecules via H-bonds into three-dimensional
(dry bubble disease in mushrooms), Pyricularia oryzae (rice blast network(Fig. 13) [38]. A salt from HQPh and cyclohexylamine
disease), Sclerotinia fruticola (apricots) and Fusarium culmorum
(cereal crops pathogen). By contrast, they are ineffective against
the insects Tribolium castaneum (Everts) and Trogoderma granarium Me
N Me
(Herbst), and only a limited ovicidal activity was registered [34].
With respect to anticancer activity, only limited data are instead N Me
Me Me
available for acylpyrazolones themselves. The previously men- O O
O O
tioned proligand H2 QPh2OH shows moderate-to-low activity against * *
human leukemia promyelocytic HL-60 and lymphoblastic NALM-6 Na Na
* *
cell lines [19], while proligand HQbiph is totally ineffective against O
O O O
human HeLa, MCF-7, HepG2, and HCT-116 cancer cell lines [35]. Me
Me Me
HQnPe and HQPh4tBu (Fig. 11) have been tested in vitro against three N
different human prostate cancer cells (DU145, LNCaP and PC-3) but Me N
n
are essentially inactive [36]. Me
[Na(QiPr)(dme)]n

Fig. 12. Structure of [Na(QiPr )(dme)]n .

F 3C
Me O H2O OH2
*
N Me Me H2O K
N OH H2O OH2
N N O O
N (CH2)8 N K
H2O N
O O N
OH O O OH Me
*
N
N
HQCF3 H2Q8Q Me n

Fig. 10. Structure of proligands HQCF3 and H2 Q8Q. Fig. 13. Structure of [K2 (QPh )2 (H2 O)3 ]n ·2nH2 O.
6 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31

Me
Me N
Et O H N Me
N N
O O N
Me Ca Me N O
N N O O O
O O O
H Et O O
Me Sc Me Sc
Me N N O O O O
N N
Ca(Q Ph4Me
)2(EtOH)2 O O
N N
N N
Fig. 14. Structure of Ca(QPh4Me )2 (EtOH)2 .
Me Me

contains QPh anions stabilized by intermolecular weak interactions

meridional isomer Sc(QPh)3 facial isomer
[38].
Fig. 15. Structures of the two isomers of Sc(QPh )3 .
4.2. Group 2: Mg, Ca, Sr and Ba

Me Me Me
Magnesium complexes Mg(Q)2 . 2H2 O (Q = QMe , QEt , QPr ) exist as
covalent octahedral complexes, containing water molecules likely N Me
coordinated to magnesium [39]. Me Me Me Me Me
N O Me
The complex Ca(QPh4Me )2 (EtOH)2 shows an octahedral calcium Me
N O O
atom bonded to the ethanol molecules and two bidentate acylpyra- Me Me Ti Me
N O Me
zolonates in an anti-configuration to each other (Fig. 14) [40]. The EtO O N
ethanol molecules are bridged together through hydrogen bond O O N
Ti Me O
EtO N N
and connect one pyrazolone-ring N(2) atom with the neighbor- O O
EtO N N
ing pyrazolone-ring N(2) atom through intermolecular hydrogen OEt Ti Me
O O
bonds, forming a three-dimensional non-planar supramolecular
framework. N O Me
Me Me
An analogous Ca(QnPe )2 (EtOH)2 displays inhibitory activity to N Me
intercellular adhesion molecule-1 (ICAM-1) [28]. Ti(OEt)2(QnPe)2
Strontium and barium complexes M(QPh4NO2 )2 . 2H2 O (M = Sr,
Me Me Me
Ba) were proposed to exist as six-coordinated species with water
molecules in apical positions and QPh4NO2 ligands in a syn config- [{Ti(OEt)(QnPe)2}2(µ-O)]
uration to each other [41]. This structural hypothesis is however
Fig. 16. Structures of Ti(OEt)2(QnPe )2 , and [{Ti(OEt)(QnPe )2 }2 (␮-O)].
quite unusual, as Sr(II) and Ba(II) ␤-diketonate complexes always
display more complex structures, reflecting the ability of such large
metal ions to expand their coordination sphere well beyond the Ti(OMe)2 (QnPe )2 [50], may be related to some weak bonds easier to
six-coordination [42]. Previous structures of Ba(II) acylpyrazolones cleave, thus favoring formation of stronger Ti-electrophile bonds,
have confirmed this trend [43], the di-hydrated complexes existing or inducing hydrolysis, and such interactions with transferrin may
as dinuclear centrosymmetric [Ba2 (Q)4 (H2 O)4 ] species, with two be critical to activity. A problem in titanium compounds is their
eight-coordinate barium atoms, terminal bidentate and bridging tendency to oligomerize, due to easy loss of the leaving groups,
tetradentate Q ligands and two water molecules. Ba(II) complexes which makes the isolation of mono and dinuclear species difficult.
with QnPe and QtBu and several polyethers and bi- and tridentate Recently, complexes such as the mononuclear (QnPe )2 Ti(OEt)2 and
N-donor ligands are instead mononuclear complexes, thanks to the dinuclear [{Ti(OEt)(QnPe )2 }2 (␮-O)] (Fig. 16), were isolated, and
multidentate ancillary donors which prevent association in the titanium is found in octahedral enviroments with two Q ligands
solid state [44]. in cis to each other, in the latter being evidence for ␲–␲ stacking
interaction between the ligands [51].
4.3. Group 3: Sc Complexes TiCl2 (QPh,Me )2 and TiCl2 (QPh,Ph )2 have been used as
catalysts, after activation with MAO (methylaluminoxane), in ethy-
The complex Sc(QPh )3 contains the Sc atom in a meridional octa- lene polymerization, however they displayed low activity [52].
hedral environment [45,46]. Two kinds of solids were obtained by
precipitation of Sc(QPh )3 from different solvents [47], possessing
different colors and melting points. Experimental and theoretical Me
Raman spectra (the latter carried out with a density functional
method) confirmed that the complex can exist in two isomers, the N Me
N
facial and meridional forms (Fig. 15). N N
O
O O O
4.4. Group 4: Ti, Zr and Hf M

Titanium complexes of classical ␤-diketones and acylpyra- N N

zolones show similar chemical and antitumor behavior. An analysis N N M = Zr, Hf
of available structural data of octahedral antitumor Ti(IV) ␤-
diketonates was undertaken by Caruso to relate such data with
the biological activity [48]: the presence of planar substitutents M(Pc)(QPh)2
and the asymmetry of the ligands, such as the Ti-O(acyl) bond
in [Ti(␮-O)(QPh )]4 [49] or those opposed to Ti-O(methoxy) in Fig. 17. Structure of M(Pc)(QPh )2 (M = Zr, Hf).
 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31 7

R1 F3C
O R3 O N N Me O
R3 N N O
O O O N N
Me O Me V O
V Me Me V N
O O O O O N
N N N N N N
R3 R 3
R1 OH2 O Me
CF3
VO(Q)2 VO(Q)2(H2O) VO(Qpy,CF3)2

QPh = R3= Ph QnPe = R1 = Ph, R3 = neopentyl

QCF3 = R3 = CF3 Q1naph = R1 = Ph, R3 = 1-naphthyl
QMe,Me = R1 = R3 = Me
QMe,1naph = R1 = Me, R3 = naphthyl

Fig. 18. Structures of VO(Q)2 , VO(Q)2 (H2 O) and VO(Qpy,CF3 )2 .

Zr(IV) and Hf(IV) mixed-ligand complexes containing phthalo- Me Me

cyaninato (Pc) and QPh exist as eight-coordinated species, where O
the presence of two pyrazolone moieties leads to stabilization of O O
the ␲-conjugated system of Pc moiety (Fig. 17) [53]. Me V Me
O O
N N N N
OH2
4.5. Group 5: V

The coordination chemistry of acylpyrazolones with vanadium VO(QPh4Me)2(H2O)

has been developed mainly for V(IV) and V(V). The reduction of oxo-
vanadium(V) by HQPh4Me in neutral and acidic conditions afforded
the anhydrous VO(QPh4Me )2 , which exists in a distorted square
pyramidal geometry with the two chelating ligands in an anti-
configuration [10j]. Oxovanadium(IV) complexes can be anhydrous
VO(Q)2 (Q = QPh , QCF3 , Qpy,CF3 ) and also monohydrate VO(Q)2 (H2 O)
(Q = QnPe , Q1naph , QMe,Me , QMe,1naph ) [54]. VO(QnPe )2 (H2 O) exists in a
distorted octahedral environment, where QnPe ligands occupy the
equatorial plane in anti-configuration to each other, and a water
molecule is trans to the oxo group (Fig. 18). By contrast, VO(Qpy,CF3 )2
contains the Qpy,CF3 ligand bonded through the N,N -chelating
arm (Fig. 18). These complexes catalyze the oxidation of styrene,
␣-methylstyrene and cis-␤-methylstyrene, in the presence of H2 O2
as oxidant [54].
The hydrate complex VO(QPh4Me )2 (H2 O), showing the QPh4Me
ligands in a syn-configuration to each other (Fig. 19), has been
impregnated onto hydrous zirconia support and the resulting het-
erogeneous material catalyzes the oxidation of styrene under mild
reaction conditions, with up to 100% conversion of styrene and
>99% selectivity for benzaldehyde [55].
The complex VO(QCH2Cl )2 (H2 O) has been covalently anchored
through its CH2 Cl group in the acyl moiety over a previously
functionalized SBA-15-NH2 silica support, affording a composite
Fig. 19. Structure of VO(QPh4Me )2 (H2 O).
material able to catalyze the oxidation bby H2 O2 of conjugated
olefins like styrene, ␣-methylstyrene and cis-␤-methylstyrene [56].
Novel complexes VO(Q)2 (H2 O), with hindered substituents in
both para- and meta-positions of the phenyl ring of Q ligands
(Fig. 20), unexpectedly contain the V O(oxo) group located cis to
the coordinated water molecule and the Q ligands are in twisted
geometry (Fig. 20), the difference with respect to previous trans
geometries being evidently due to the methyl groups in para posi-
tion of the phenyl bonded to N1 of pyrazolone [57].
A mixed ligand vanadyl cationic complex
[VO(QH )(bipy)(H2 O)]ClO4 (Fig. 21) displays antibacterial activity
against S. aureus, E. coli, and P. aeruginosa [17].
The complex [VO(QsQ)(H2 O)]n .H2 O, containing a potentially
tetradentate ligand QsQ, is a coordination polymer (Fig. 22) [58].
The same ligand QsQ afforded coordination polymers with other
transition metal ions [58].
A comparative study of experimental and theoretical results of
conformations for some oxovanadium(IV) complexes with Q lig-
ands using DFT method reported the optimized structures and

R3 R3
Me
O
O O N
Me V Me
O O N
N N N N O
OH2 O O
Me V
R2 O OH2 Me
R2 R1 R1 N N
O
VO(Q)2(H2O)
Me
QPh4Me = R1 = R2 = H, R3 = Me
VO(QPh4Me,Ph)2(H2O)
QPh4Me,Ph4Me = R1 = Me, R2 = H, R3 = Me
QPhCl2,Ph4Me = R1 = R2 = Cl, R3 = Me
QPhCl2,Ph = R1 = R2 = Cl, R3 = H

Fig. 20. Structures of VO(Q)2 (H2 O) and VO(QPh4Me,Ph )2 (H2 O).

8 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31

O O Me
H
O N N
Me V
O N O N
N N ClO4- O
OH2 O O
Me Cr
N N O O
O
N
[VO(QH)(bipy)(H2O)]ClO4
N
Fig. 21. Structure of [VO(QH )(bipy)(H2 O)]ClO4 . O Me

N N
N N
N N
O O H H O O
O O
V V
H2O H2O
O O O O
N N
N N
[VO(QsQ)(H2O)]n.H2O
Fig. 22. Structure of polymeric [VO(QsQ)(H2O)]n ·H2 O.
electronic properties of hydrate complexes VO(Q)2 (H2 O) calculated
for both the syn and anti-conformations [59].
meridional isomer
Cr(Qfur)3
Fig. 23. Structure of Cr(Qfur )3 .
and isomer A results the most stable, from an energetic point of
n view, with respect to isomers B and C. The crystal structures of
MoO2 (QEtCp )2 and MoO2 (QHe )2 correspond to the most stable iso-
mer A. All Mo(IV) complexes are efficient catalysts for selective
deoxygenation of styrene epoxide to styrene [61].
The complex WO2 (QPh4NO2 )2 ·2H2 O is likely octahedral with the
two W O(oxo) groups in trans positions, but no conclusive proofs
was reported about which conformation of QPh4NO2 ligand (syn or
anti) is adopted in the solid state [62].

4.6. Group 6: Cr, Mo and W

The Cr(III) complex Cr(Qfur )3 has been obtained under solvother-
mal conditions [60] and the Cr atom is octahedrally coordinated,
with the Qfur ligands defining the meridional geometric isomer
(Fig. 23).
Such complex makes a one-dimensional (1D) zigzag chain
structure by intermolecular ␲–␲ interactions, which is further
interlinked via C H· · ·N H-bonding interactions to generate a 2D
sheet, and then a three-dimensional (3D) supramolecular network
structure is further linked by intermolecular C H· · ·␲ interactions.
The complexes MoO2 (Q)2 (Q = QCy ,QEtCp , QHe , and QnPe ) show
catalytic activity on deoxygenation of selected epoxide substrates
to alkenes in toluene, by employing PPh3 as the oxygen acceptor
[61]. Being the acylpyrazolones asymmetric ligands, three isomers
are possible (Fig. 24), without consideration of the corresponding
enantiomers. They have been analyzed by using DFT calculations
4.7. Group 7: Mn
Manganese coordination chemistry with acylpyrazolones
has been expanded in recent years mainly with Mn(II) and
Mn(III) acceptors. Two mononuclear cationic complexes
[Mn(Q)(bipy)(OAc)]ClO4 (Q = QH and QPh4Me,H ) exist in a five-
coordinate square pyramidal environment, with the acetate ligand
bonded to Mn in an asymmetric monodentate fashion (Fig. 25).
They react with o-phenelendiamine or p-phenelendiamine
affording dinuclear Mn(II) complexes of tetradentate Shiff bases
[63].
The complex Mn(QPh )2 (MeOH)2 is octahedral with two
methanol molecules trans to each other and the QPh ligands
adopting the anti-configuration [64]. Similar Mn(II) complexes
Mn(Q)2 (H2 O)2 , with Q = QPhNO2 and QH possess structures with two
water molecules in trans positions of the octahedron [62,65].

Me
N N
Me N Me N R3
N
O O N O
R3 O R3 O O O
O O
Mo Mo Mo
O O O O O O
R3
O N O N O

N N N
Me N R 3
R3
Me Me

isomer A isomer B isomer C

QCy = R3 = cyclohexyl,
QnPe = R3 = neopentyl,
QEtCp = R3 = CH2CH2-cyclopentyl,
QHe = R3 = hexyl

Fig. 24. Possible isomers for MoO2 (Q)2 complexes.

 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31 9

Me sodium azide affording (cymene)Ru(QnPe )N3 , and the chlo-

O
O donor ligands such as triphenylphosphine, 1-methylimidazole,
H
O N
Me Mn
O N ClO4-
N N
X
HQH, X = H
HQPh4Me,H, X = Me
Fig. 25. Structure of Mn(Q)(bipy)(OAc)]ClO4 .
4.8. Group 8: Fe and Ru
Iron chemistry with acylpyrazolones continue to be very scarce,
and only two paper are present in the period 2005–2015 dealing
on coordination of acylpyrazolones with iron acceptors. A novel
complex Fe(QPh4NO2 )3 has been proposed to exist in the solid state
in a tris-chelate octahedral geometry [62]. Acylpyrazolone and
bis(acylpyrazolones) act as iron chelators, with high affinity for
Fe(III) ions and different affinity for Fe(II) ions [31].
Much more developed is instead the chemistry of acylpyra-
zolones with ruthenium, in particular with arene-Ru(II) accep-
tors. Monomeric (arene)Ru(Q)Cl complexes adopt the clas-
sic half sandwich piano stool geometry, while a dimeric
[{Ru(cymene)Cl}2 (Q4Q)] exists in the RRuSRu (meso form) (Fig. 26)
[66]. The ligand Qpy,CF3 chelates the metal center through the N,N-
chelating arm (Fig. 26).
Complexes (arene)Ru(Q)Cl are chiral-at-metal and can exist
as a pair of enantiomers. (cymene)Ru(QnPe )Cl reacts with
ride can be displaced also by other neutral monodentate
or 1-methyl-2-mercaptoimidazole. In the presence of AgSO3 CF3
or AgClO4 , exo-bidentate ditopic ligands L L (4,4 -bipyridine
and bis(diphenylphosphino)propane) lead to ionic mononuclear
[(cymene)Ru(QnPe )L]X (X = SO3 CF3 or ClO4 ) and ionic dinuclear
[{(cymene)Ru(QnPe )}2 (L L)]X2 [66].
The azido complexes (arene)Ru(QPh )N3 undergo a [3 + 2]
cycloaddition reaction of the azide with the activated alkynes
dimethyl and diethyl acetylenedicarboxylates, producing the
corresponding triazolato complexes (arene)Ru(QPh )(triazolato)
(Fig. 27) [67].
Water soluble neutral (arene)Ru(Q)Cl and ionic
[(arene)Ru(QPh )X]PF6 (arene = cymene, benzene, hexamethylben-
zene; Q = QMe,Me , QMe,Ph , and QMe,2naph ; X = H2 O, 9-ethylguanine)
show antitumor activity in vitro toward MCF7 (human breast
adenocarcinoma), HCT116 (human colorectal carcinoma),
A2780 (human ovarian carcinoma), A549 (human lung car-
cinoma), and U87 MG (human glioblastoma) [68]. Among
them, (cymene)Ru(QMe,2naph )Cl shows an activity systemati-
cally higher than the others in all cell lines. The structure of
(cymene)Ru(QMe,2naph )Cl was also studied with DFT methods
and selected for docking on a DNA octamer, showing interca-
lation between DNA bases by the 2-naphthyl moiety and for
Ru–N7(guanine) bonding [68].
Other (arene)Ru(Qbiph )Cl complexes, and the ionic compounds
with 1,3,5-triaza-7-phosphaadamantane (PTA) (Fig. 28), display
antiproliferative activity against four human cancer cell lines
[35], the hexamethylbenzene–Ru(II) complexes being the more
active. Apoptosis seems the mechanism involved in the anticancer
activity, in fact the hexamethylbenzene–Ru(II) complexes activate
caspase activity, followed by DNA fragmentation, accumulation

arene arene

Cl Ru Ru Cl Me
O Ru
Ru N
R3 O O O
Cl O O Cl
O F3C N N
O
Me
N N R1 N N
N Me Me N

(arene)Ru(Q)Cl [{(cymene)RuCl}2(Q4Q)] (arene)Ru(Qpy,CF3)Cl

(QnPe = R1 = Ph, R3 = neopenthyl; QMe,nPe = R1 = Me, R3 = neopenthyl; Q1naph = R1 = Ph, R3 =

1-naphthyl; QCF3 = R1 = Ph, R3 = CF3; arene = cymene or benzene)

Fig. 26. Structures of (arene)Ru(Q)Cl, [{Ru(cymene)Cl}2 (Q4Q)] and (arene)Ru(Qpy,CF3 )Cl.

arene arene

Ru Ru
O O
N3 N N D
O O
N
Me Me
N N N N C

(arene)Ru(QPh)N3 (arene)Ru(QPh)(triazolato)

(arene = cymene or benzene; C = D = COOEt or COOMe; C = H, D = CN)

Fig. 27. Structures of (arene)Ru(QPh )N3 and (arene)Ru(QPh )(triazolato).

10 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31

arene
arene

arene = cymene, benzene Ru

Ru and hexamethylbenzene O
O X PF6-
Cl O
O Me
Me X = MeOH, PTA N N
N N

(arene)Ru(Qbiph)Cl [(arene)Ru(Qbiph)X]PF6

Fig. 28. Structures of (arene)Ru(Qbiph )Cl and [(arene)Ru(Qbiph )X]PF6 (X = MeOH, PTA).

octahedral, with the monodentate ligands in apical positions and

N Me
N
O dron around Co surprisingly displays the two ethanol molecules in
Me O O
Ru
N N O Some of previous complexes have been obtained by solvother-
PPh3
PPh3
Ru(QiPr)2(PPh3)2
Fig. 29. Structure of Ru(Q iPr )2 (PPh3 )2 .
of pro-apoptotic proteins (p27, p53, p89 PARP fragments),
and the concomitant down-regulation of antiapoptotic protein
Bcl-2 [35].
The complex Ru(QiPr )2 (PPh3 )2 is in a distorted octahedral envi-
ronment,where QiPr ligands, as well as PPh3 , are cis to each other
(Fig. 29). It is able to initiate metathetical norbornene polymeriza-
tion into high molecular weight polynorbornenes [37].
Complexes [{(arene)RuCl}2 (Q(spacer)Q)] (arene = cymene and
hexamethylbenzene; Q(spacer)Q = Q3Q, Q(1,3-ph)Q and Q(1,4-
ph)Q) are dinuclear species, with the Q(spacer)Q acting in a
bis(chelating) bridging fashion (Fig. 30) [69]. They are cytotoxic
toward epithelial cancerous HeLa and MCF7 cell lines to a com-
parable extent to cisplatin but with higher capacity to discriminate
between normal MDCK cells and cancer cells.
4.9. Group 9: Co, Rh and Ir
The coordination chemistry of acylpyrazolones with cobalt
has been expanded in the last years, several Co(Q)2 (H2 O)2 com-
plexes (Q = QMe : R3 = CH3 , QEt : R3 = CH2 CH3 , QPr : R3 = CH2 CH2 CH3 ,
QPe : R3 = (CH2 )4 CH3 , QPd : R3 = (CH2 )14 CH3 ) being published [70].
The complexes Co(QMe )2 (EtOH)2 [71], Co(Qfur )2 (MeOH)2 [59],
(fur = furyl) Co(QPe )2 (H2 O)2 [72], and Co(QH )2 (py)2 [65], are
the two Q adopting the anti-configuration (Fig. 31). By contrast,
in Co(Qthi )2 (EtOH)2 (thi = thiofene), the slightly distorted octahe-
mutual cis positions (Fig. 31) [73].
mal synthesis and others in normal conditions, but this aspect does
not seem responsible of the different cis or trans geometry found
in the solid state. More subtle reasons should be involved in such
differences, but at the moment no clear explanation has been pro-
posed.
The complex Co(QNO )2 (H2 O)2 containing a novel O,O -chelating
acylpyrazolone, has been obtained by solvothermal reaction of 3-
methyl-1-phenyl-5-pyrazolone and Co(NO3 )3 in acetonitrile, and
exists in a slightly distorted octahedral geometry with the two
QNO ligands in the equatorial plane adopting the anti-configuration,
while two coordinated water molecules are in the axial positions
(Fig. 32) [74]. The QNO ligand is generated in situ through the
nitration of 3-methyl-1-phenyl-5-pyrazolone mediated by cobalt
nitrate, affording the complex Co(QNO )2 (H2 O)2 [74].
A plausible nitration mechanism for the electrophilic substi-
tution of the starting pyrazolone has been proposed (Fig. 33),
involving nitrate salt as nitrating agent: each nitrate group is ini-
tially coordinate to metal center through one O atom per nitrate
group, and can accept protons to form nitric acids, in which each
hydroxyl group accepts another proton to give one protonated
water. Consequently, the protonated water is dehydrated to yield
nitroxyl cation NO2 + . Then, NO2 + cation acts as electrophilic reagent
and attacks C4 position of the pyrazole ring to form an unsta-
ble intermediate, which is soon deprotonated giving the nitration
product [74].
Rhodium(III) and iridium(III) complexes [(Cp*)M(Q)Cl]
(Cp* = pentamethylcyclopentadienyl; M = Rh or Ir, Q = QMe , R = Me;
QEt , R = Et; HQnPe , R = CH2 C(CH3 )3 ; QBn , R = CH2 (C6 H5 ); QCHPh2 ,
R = CH(C6 H5 )2 ) show a classic half-sandwich geometry on the
metal atom (Fig. 34) [75]. The presence of AB quartets in 1 H NMR
spectra of complexes with QEt , QnPe and QBn ligands are due to

Q2Q: spacer = -CH2CH2-

Cl Ru Ru Cl
O O
O O Q(1,3-ph)Q: spacer =
(spacer)
N N
N Me Me N
Q(1,4-ph)Q: spacer =

[{(cymene)RuCl}2(Q4Q)]

Fig. 30. Structure of [{(arene)RuCl}2 (Q(spacer)Q)].

 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31 11

of Ir(dbzm)(ppy)2 (dbzm = dibenzoylmethane), due to the higher

S triplet energy level of QiPr relative to that of dbzm [77]. Other
N
R3 N N Me N
O cyclometalated quinoline complexes Ir(QiPr )(N-C)2 (N-C ligands
Me O
Co Me are quinolone substituted ligands shown in Fig. 35) are phos-
O O S O Et
N N phorescent emitters with high quantum efficiencies lifetimes, a
R3 O H
S O
Co significant spin-orbit coupling of the iridium center, and quantum
O O H efficiency higher than that of analogous Ir(III) acetylacetonato
Co(Q)2(S)2 S O Et complexes with the same quinolone derivatives [78].
Ir(QMe )(N C)2 complexes (N-C = 4-methyl-2,3-
Me N
N diphenylquinoline and 2,3-bis-(4-fluorophenyl) quinoxaline)
(Q = QMe, R3 = CH3; Qfur R3 = furyl;
display red emission [79]. Other Ir(Q)(N-C)2 complexes (Q = QPh ,
QH, R3 = H; QPe, R3 = (CH2)4CH3;
QPh4Me , QPh4Cl , QPh4F , QPh4NMe2 , Q2naph ; N-C = 4-methyl-2,3-
S = H2O, MeOH, EtOH or py) Co(Qthi)2(EtOH)2
diphenylquinoline and 2,3-bis-(4-fluorophenyl)quinoxaline)
Fig. 31. Structures of trans Co(Q)2 (S)2 and of cis Co(Qthi )2 (EtOH)2 . (Fig. 36) show the expected octahedral geometry on Ir(III) atom
[80], and are red photo- and electroluminescent [81].
The complexes Ir(Qpy,R3 )(dfppy)2 (R3 = CF3 , Ph, Bn, Ph4F, naph;
OH2 dfppy = (2,4-difluoro)phenylpyridine) interact with EuCl3 . 6H2 O
O
N N affording Ir–Eu bimetallic derivatives, where the Qpy,R3 ligands act
N O O as bridging N,N -O,O -tetradentate donors, the O,O -chelating face
Me Co
O Me
N N O N being coordinated to Eu(III) atom (Fig. 37) [15]. All complexes are
OH2 O photoluminescent, and a photophysical investigation of bimetallic
complexes in solution indicates that the bridging Qpy,R3 ligands play
an important role in the electron transfer process: only when the
Co(QNO)2(H2O)2 triplet energy level of the bridging ligand is lower than the triplet
metal-to-ligand charge transfer energy level of the Ir(III) moiety, a
Fig. 32. Structure of Co(QNO )2 (H2 O)2 .
pure emission from the Eu(III) ion is observed [15].
The complex Ir(Qnorb )(ppy)2 (Fig. 38) undergoes metathesis
diastereotopic CH2 in ␣ position of the 4-acyl carbonyl, in polymerization and forms new iridium-containing co-polymers,
accordance with the existence of enantiomers (Fig. 34). Reac- whose luminescence is caused by the MLCT transitions in the
tion of (Cp*)Rh(QMe )Cl with silver salts AgX (X = NO3 or ClO4 ) iridium-containing fragments [10g].
affords ionic solvated [(Cp*)Rh(QMe )(solv)]X (solv = H2 O, X = ClO4 ;
solv = MeCN, X = NO3 ). An excess PPh3 displaces the chloride 4.10. Group 10: Ni, Pd and Pt
affording [(Cp*)Rh(Q)(PPh3 )]Cl (Q = QMe , QBn , QCHPh2 ) [75].
The cyclometalated complex Ir(QPh,Ph,Bn )(tpq)2 (tpq = 2- The complexes Ni(Qfur )2 (EtOH)2 [82] and Ni(QMe )2 (DMF)2 [83]
(thiophen-2-yl)quinoline) (Fig. 35) shows a characteristic (Fig. 39) exist in an octahedral geometry with the solvent molecules
phosphorescence in solution with a high quantum efficiency in apical positions and the two Q ligands in anti-configuration.
and has been used as dopant in the fabrication of a saturated The complex Ni(QNO )2 (H2 O)2 (Fig. 39), containing the previously
red polymer-based electrophosphorescent device [76]. Another mentioned QNO ligand, has been obtained by in situ nitration of 3-
cyclometalated complex Ir(QiPr )(ppy)2 (ppy = 2-phenylpyridine) methyl-1-phenyl-5-pyrazolone in acetonitrile under solvothermal
(Fig. 35) displays a solid state green emission higher than that conditions [74].

O HO H2O
N O O O
H N N
N N N
N O O O O O N O O
N O + 2H+ O
Co O N Co Co
O N O N
O OH OH2
O H O O

N N N N N N

- 2H2O

O O
N OH2 H N N O
O OH2 N
N O N O O
N O
N O Co O - 2H+ + 2H2O
N N O Co O Co N
N O
O N
H2O O N O
N H2O
N
H
O N
O N

Fig. 33. Nitration mechanism and in situ formation of QNO ligands.

12 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31

Me
Me Me Me Me Me Me
R3 R3
Me Me O Me Me O
M Me Me
R3 O Me M M Me
Cl Me O N N O Me
O Cl N N Cl
Me
N N (Cp*)M(Q)Cl

(M = Rh or Ir, Q = QMe, R = Me;

enantiomers
QEt, R = Et; QnPe, R = CH2C(CH3)3;
QBn, R = CH2(C6H5); QCHPh2, R = CH(C6H5)2)

Fig. 34. Structure of (Cp*)Rh(Q)Cl and their enantiomers.

Me Me Me Me
Me Me
N N
N O O
N N
O N
N O O
O N
N Ir Ir
Ir N N
C
S N C

Ir(QPh,Ph,Bn)(tpq)2 Ir(QiPr)(ppy)2 Ir(QiPr)(N-C)2

N N N N N N
N-C ligands are:

C6H13
C6H13

Fig. 35. Structures of Ir(QPh,Ph,Bn )(tpq)2 , Ir(QiPr )(ppy)2 and Ir(QiPr )(N C)2 .

Me
R3 N-C ligands are:
N
O N
N
N O
Ir
C N
C
4-methyl-2,3-diphenylquinoline
Ir(Q)(N-C)2

(Q = QPh, QPh4Me, QPh4Cl, QPh4F, QPh4NMe2, Q2naph)

N N

R= Me Cl

F NMe2 F F
2,3-bis-(4-fluorophenyl)quinoxaline

Fig. 36. Structure of Ir(Q)(N C)2 complexes.

 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31 13

O
N N O
N N
N N
R3 Ir
Ir F N
F N Me N O
R3 = -CF3 F EuCl.2Cl-
O
F F 3
F 2
F
Ir(Qpy,R3)(dfppy)2 bimetallic Ir–Eu complexes

Fig. 37. Structure of Ir(Qpy,R3 )(dfppy)2 and of Ir–Eu bimetallic complexes.

K2 [MCl4 ] with H2 Qpy,PhOH in 1:1 molar ratio in DMF, the com-

plexes Me2 NH2 [MCl2 (HQpy,Ph2OH )] were isolated (Fig. 40), where
Me
the cation [Me2 NH2 ]+ is formed by light-induced decomposition
N of DMF and protonation of the arising dimethylamine. The com-
O N plex PdCl(HQpy,Ph2OH )(MeCN) (Fig. 40) afforded from reaction of
O PdCl2 (PhCN)2 with H2 Qpy,Ph2OH in 1:1 molar ratio.
N Their cytotoxic activity in vitro against HL-60 and NALM-6
Ir
N leukemia cell lines is similar to that of carboplatin. The alkylating
activity of PtCl2 (H2 Qpy,Ph2OH ) is comparable to those of cisplatin and
carboplatin [19].
The complex Pt(Qnorb )(ppy) (Fig. 41) copolymerizes with a
carbazole containing norbornene co-monomer by ring-opening
Ir(Qnorb)(ppy)2 metathesis polymerization (ROMP) [84]. The photo- and electro-
luminescence of the resulting Pt-copolymer (Fig. 41) are similar
Fig. 38. Structure of Ir(Qnorb )(ppy)2 . to those Pt(Qnorb )(ppy), and arise from the mixed ligand centered
(LC) and metal to ligand charge transfer (MLCT) transitions. The
platinum-containing copolymer has been employed as emitting
Pd(II) and Pt(II) complexes with the proligand H2 Qpy,Ph2OH are material in three-layer OLED device, which produces white light
potential anticancer compounds [19]. Those with the proligand [84].
in its neutral form, MCl2 (H2 Qpy,Ph2OH ) (M = Pd or Pt) (Fig. 40) An analogous Pt(QiPr )(ppy) (Fig. 42) possesses electrolumines-
were prepared by mixing equimolar amounts of the proligand cent properties and has been tested on model OLED devices [85].
and K2 [MCl4 ] (M = Pd or Pt). By contrast, from reactions of The complex Pt(QiPr )(dfppy) (Fig. 42) contains dimeric units where

S OH2
R3 O
N N
N N N O
Me O O Me O
Ni Me Ni Me
N N O O N N O O N
3 O
S R OH2

Ni(Q)2(S)2 Ni(QNO)2(H2O)2

Q = Qfur, S = EtOH
Q = QMe, S = DMF

Fig. 39. Structure of Ni(Q)2 (S)2 and Ni(QNO )2 (H2 O)2 .

HO HO HO
O O O
Me Me Me Me
Me C
Cl N Cl N N N
OH H N O N OH
N H N
M M Pd
Me
Cl N Cl N Cl N

(M = Pd or Pt)

MCl2(H2Qpy,Ph2OH) Me2NH2[MCl2(HQpy,Ph2OH)] PdCl(HQpy,Ph2OH)(MeCN)

Fig. 40. Structures of MCl2 (H2 Qpy,Ph2OH ), Me2 NH2 [MCl2 (HQpy,Ph2OH )] (M = Pd or Pt) and PdCl(HQpy,Ph2OH )(MeCN).
14 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31

*
m n

N O O N
(CH2)5
Pt Me Me Pt
O N O
N N N N

Pt(Qnorb)(ppy) carbazole-containing Pt(II) copolymer

Fig. 41. Structures of Pt(Qnorb )(ppy) and of carbazole-containing Pt(II) copolymer.

Me Me Me
Me N O Me
Pt
N O F O N N
Pt Me
O F
Me
N N O
Me
N Pt Me
F O N N

F
Pt(QiPr)(ppy) Pt(QiPr)(dfppy)

Fig. 42. Structures of Pt(QiPr )(ppy) and of dimer Pt(QiPr )(dfppy).

the Pt-Pt distance is significantly smaller than the sum of the Van
der Waals radii of Pt [86].
The complex trans-PtCl2 (HQPh )(dmso) crystallizes in
two polymorphic forms, corresponding to trans–syn and
trans–anti-conformers (Fig. 43) [87]. The asymmetric unit of
cis-PtCl2 (KQpy,CF3 )·H2 O consists of the anionic complex cis-
[PtCl2 (Qpy,CF3 )]− , one K+ counter cation, and one crystallization
water molecule (Fig. 43). All complexes are sufficiently soluble
in water and display anticancer activity against human cervix
carcinoma (HeLa) and human breast carcinoma (MCF-7) [87]. The
trans-PtCl2 (HQPh )(dmso) shows higher cytotoxicity on HeLa cells
compared to cis-PtCl2 (HQPh )(dmso). This is an unexpected and
interesting result, because the trans isomer of cisplatin has no
biological activity [87].
4.11. Group 11: Cu and Ag
The complexes Cu(Q)2 (Q = QPh4Me , X = Y = H; QPh3Cl,Ph4Me , X = H,
Y = Cl; QPh4Me,Ph4Me , X = Me, Y = H) exist in the expected square
planar geometry, with the two Q ligand in anti-configuration
(Fig. 44) [40].
They interact with pET30a plasmid DNA (a bacterial expression
vector isolated from E. coli) via an intercalative mode. They also
show antibacterial activity against Gram positive (B. subtilis) but
not against Gram negative (E. coli) [40].
Attempts to crystallize Cu(QH )2 ·1.5H2 O from methanol–
pyridine afforded the complex Cu(QH )2 (py)2 , containing a distorted
octahedral environment with two pyridine in apical positions and
the QH ligands in anti-configuration [65]. The solid state structure
of other Cu(Q)2 (H2 O)2 (Q = QMe , QEt , QPr ) likely resembles that of
Cu(QH )2 (py)2 [39].
Mixed ligand Cu(II) complexes CuNCS(QPh4Me )(N N) (N-
N = phen or bipy) possess slightly distorted square-pyramidal
structures (Fig. 45) [88]. Their interaction with calf thymus DNA
occurs through intercalation. They also interact with bovine serum
albumin, and are cytotoxic againts human lung cancerous cell line
(A549) and noncancerous rat cardiomyoblasts (H9C2) cell lines
[88].
The crystal structure of Cu(QiPr )(dpephos) (dpephos = bis[2-
(diphenylphosphino)-pheny]ether) reveals a classic tetrahedral
environment of copper with a O,O -chelating QiPr and the P,P -
chelating dpephos (Fig. 46), whereas complex Cu(QtBu )(dpephos)
contains a 3-coordinate copper atom with an unusual ␩1 coordina-
tion of QtBu ligand through the N atom of pyrazole ring (Fig. 46)
[89]. These Cu(I) complexes show dual emission consisting of
bands assigned to transitions from the S1 and T1 states. They

O
O F Me
Me Cl F C
Me O F
F N
S Me K O N Cl
HO N H2O Pt
N Pt O
Me Cl
Cl N S Me
O Me O OH2 O
Cl F3C Me
Cl
H N N
O N Pt Me O Cl cis-PtCl2(KQpy,CF3)
N
S Ph Pt
O cis-PtCl2(HQ )(dmso)
Cl Me N S Me
Me O

trans-PtCl2(HQPh)(dmso) cis-PtCl(Qpy,CF3)(dmso)

Fig. 43. Structures of cis and trans PtCl2 (HQPh )(dmso), cis-PtCl(Qpy,CF3 )(dmso) and cis-PtCl2 (KQpy,CF3 ).
 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31 15

X Y
Me

N N
O O QPh4Me, X = Y = H;
Me Cu Me
O O QPh3Cl,Ph4Me, X = H, Y = Cl;
N N QPhMe,Ph4Me, X = Me, Y = H;

Me
Y
X
Cu(Q)2

Fig. 44. Structure of Cu(Q)2 .

Me Me Such complexes interact with N-donor ligands L (L = imidazole,

O N O N
Me Cu Me Cu
N N O N O N
N N
N N
C C
S S
CuNCS(QPh4Me)(N-N) (N-N = phen or bipy)
Fig. 45. Structures of CuNCS(QPh4Me )(N N) (N N = phen or bipy).
are also able to generate electroluminescence of yellowish-orange
(Cu(QiPr )(dpephos)) and yellow (Cu(QtBu )(dpephos)) colors.
Copper(I) complexes Cu(Q)(PPh3 )2 (Q = QCF2CF3 , QPh4CF3,CF3 ,
1naph
Q , Qfur , Qthi , Qpy,CF3 ) are isostructural and conform to distorted
tetrahedral copper environments (Fig. 47) [90].
Apart from Cu(Q1naph )(PPh3 )2 , all the others are fluxional in
chloroform solution and partially dissociate into the [Cu(Q)(PPh3 )]
fragment and free PPh3 . In the complex Cu(Qpy,CF3 )(PPh3 )2 , the
Qpy,CF3 ligand chelates copper through the nitrogen atoms of the
pyrazole and pyridine rings (Fig. 47). This complex interacts with
Zn(BF4 )2 ·xH2 O and [Ru(p-cymene)Cl2 ]2 through the O,O -chelating
face affording ionic heterobimetallic adducts (Fig. 48) [90].
Silver(I) complexes with acylpyrazolones can exist as neutral
mononuclear, polynuclear, or ionic species, as a function of the
ancillary azole ligand used in the synthesis [12]. From interaction of
AgNO3 and HQ (HQ = HQPh or HQpy,CF3 ), two silver insoluble coordi-
nation polymers [Ag(Q)]n were isolated and their polynuclear solid
state structure identified by a combination of solid state spectro-
scopic techniques, the N atom(s) of the Q ligand being bonded to
silver (Fig. 49).
1-methylimidazole, 2-ethylimidazole, 1-benzylimidazole, 2-
methyl-1-benzylimidazole, 2-trifluoromethyl-benzimidazole,
di(1H-imidazol-1-yl)methanone, 2,4,6-trimethylpyridine), afford-
ing Ag(Q)(L) or Ag(Q)(L)2 type-complexes, where the latter can
exist in the solid state as neutral or ionic species (Fig. 50)[12].
The dinuclear complex [{Ag(Qpy,CF3 )}(COdim)] (COdim = di(1H-
imidazol-1-yl)methanone) decomposes in acetone/chloroform
solution, affording the monomeric specie [Ag(Qpy,CF3 )(imH)]
(Fig. 50).
All complexes were embedded in polyethylene (PE) matrix, and
most of the resulting PE composites show antimicrobial activity
against three bacterial strains (E. coli, P. aeruginosa, and S. aureus),
comparable to PE embedded with AgNO3 [12]. At least in the case of
PE composites containing polynuclear [Ag(Q)]n , the antimicrobial
action seems exerted by contact, without release of silver ions. The
PE composites can be re-used several times, displaying the same
antimicrobial activity, and are not cytotoxic toward human cells.
Studies of ecotoxicity confirms also tolerability of the PE compos-
ites by higher organisms and exclude the release of Ag+ ions in
sufficient amounts to affect water environment [12].
4.12. Group 12: Zn
In the complexes Zn(Qfur )2 (ROH)2 (R = Me or Et) the Zn atom is in
an inversion center of a distorted octahedral geometry, where the
two ethanol molecules are mutually trans, while the two bidentate
Qfur ligands adopt an anti-configuration (Fig. 51) [91]. Two com-
plexes Zn(Q)2 (H2 O)2 (Q = QtBu or QnPe ) display ICAM-1 inhibitory
activity [28].
Heteroleptic Zn(II) complexes Zn(Q)2 (N N) and
ZnCl(Q)(N N)(H2 O) (Q = QPh4tBu or QnPe ; N-N = 4,4 -dinonyl-
2,2 -bipyridine) (Fig. 52) are active in vitro against three different
human prostate cancer cells, DU145, LNCaP and PC-3 [36].

P P
Me O O
Me O Cu Cu
N N
Me O P P
O
N N
Me
Me O
Me

Cu(QiPr)(dpephos) Cu(QtBu)(dpephos)

Fig. 46. Structures of Cu(QiPr )(dpephos) and Cu(QtBu )(dpephos).

16 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31

R3
Me O
O
PPh3 Me
Cu F3C
N O
N PPh3 N
QCF2CF3, R3 = CF2CF3, X = H O N PPh3
QPh4CF3,CF3, R3 = CF3, X = CF3 Cu
Qfur, R3 = C4H3O, X = H N PPh3
Qthi, R3 = C4H3S, X = H
X Q1naph, R3 = 1-naphthyl, X = H
Cu(Q)(PPh3)2 Cu(Qpy,CF3)(PPh3)2

Fig. 47. Structures of Cu(Q)(PPh3 )2 and Cu(Qpy,CF3 )(PPh3 )2 .

Me PPh3 2+
F3C
N Cu PPh3 Me +
Me
F3C O N Me
N
O O
Me Ru
Zn O CF3
O O Cl
N O
N CF3 (BF4-)2 PF6-
O Me
Ph3P Cu N N
N
Ph3P N Me
N N Cu
N PPh3
Cu PPh3
PPh3
Ph3P
[(p-cym)RuCl{Cu(Qpy,CF3)(PPh3)2}]PF6
[Zn{Cu(Qpy,CF3)(PPh3)2}3](BF4)2

Fig. 48. Structures of heterobimetallic Cu–Zn and Cu–Ru adducts.

O
F3C
O N
Ph * O Ag *
N N N
* Ag O N Ag O N * N N
N Ag O
Ph
N
O F3C
n O n
[Ag(QPh)]n [Ag(Qpy,CF3)]n

Fig. 49. Structures of coordination polymers [Ag(QPh )]n and [Ag(Qpy,CF3 )]n .

Other heteroleptic ZnCl(QPh4tBu )(L L) and Zn(QPh4tBu )2 (L L)
(L L = 4,4 -bis[3,4,5-(tri-hexadecyloxy)benzoyloxymethyl]-2,2 -
bipyridine or 4,7-bis[3,4,5-(tri-hexadecyloxy) benzoyloxymethyl]-
1,10-phenanthroline) (Fig. 53) display green luminescence which
is retained also in the mesophase and even in the isotropic state,
with a general and reversible red-shift related to the increase of
temperature [92].
Other Zn(II) complexes Zn(Q)2 (H2 O)2 (Q = QPh4NO2 , QMe , QEt ,
QPr ) [39,41] have the same structure as that shown in Fig. 51.
Wheres, the complexes Zn(Q)2 (H2 O) (Q = QEt , QPh3Cl,Et ) contain a
five-coordinated zinc with water in the axial position and the
Q ligands in anti-configuration, and Zn(QEt )2 (phen) (phen = 1,10
phenanthroline) is octheral with a chelating phen ligand (Fig. 54)
[93]. They form adducts with DNA and distort the double helix by
changing the base stacking.
The complex Zn(QHe )2 (H2 O) adopts a square pyramidal geom-
etry on zinc, with an apical water molecule but, unexpectedly,
the QHe ligands in a syn-configuration (Fig. 54) [94]. This complex
exhibits antibacterial activity in vitro against 4 human pathogenic
bacteria (B. subtilis, E. coli, S. epidermidis, and S. aureus), moreover
it displays purple emission as the result of fluorescence from the
intraligand emission excited state.
ZnO nanoparticles, decorated by molecules of a long chain
acylpyrazolone QHd ligand, namely 1-phenyl-3-methyl-4-
octadecyl-5-pyrazolone (Fig. 55) have been used to form a
quasi-solid-state electrolyte and employed in dye sensitized solar
cell (DSSC). Since the long alkyl-chain of the acylpyrazolone
interacts with liquid solvent, the quasi-solid-state DSSC with
the decorated nanoparticles shows higher stability in compar-
ison with that of the liquid device with a comparable overall
efficiency [95].
4.13. Group 13: B and Al
Fluorine–boron BF2 (Q) complexes (Q = QMe , QPh,Ph,Me , QPh,Ph,Ph )
(Fig. 56) display a luminescence related to the solid state struc-
ture: well-ordered molecular packing in the crystal results in strong
 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31 17

Me
N O
O O N
Me Me O
H
Me N N N N
N Ag N N O Ag N O
N
N Ag N
N H
N H
X N N
Me N Ag N
N
(X = H or Bn) Ph Ph H
Ag(Q )(L) Ag(Q )(Meim)2 O
N
O N
O Me
F3C Ag(Qpy,CF3)(L) [Ag(imH)2]2(QPh)2
O N
N Ag L L = trifluoromethyl-benzimidazole, 2-ethylimidazole,
N 1-benzylimidazole, 2-methyl-1-benzylimidazole,
2-2,4,6-trimethylpyridine

O O
F 3C O F3C
N O N
O N N N N Ag N
N Ag N N Ag N
N O N
N Me
N
CF3
[{Ag(Qpy,CF3)}(COdim)] O Ag(Qpy,CF3)(imH)

Fig. 50. Structures of mononuclear Ag(Q)(L) and Ag(Q)(L)2 , and of dinuclear [{Ag(Qpy,CF3 )}(COdim)].

H Et or benzoylacetone) (Fig. 59) have been prepared by using 1:1:2 and

O
O N N 1:2:1 molar ratios [99].
Me O O
O Zn O Me
N N O 4.14. Group 14: Sn and Pb
O
Et H
Dibutyltin(IV) mixed ligand complexes Bu2 Sn(Q)(aac) (Q = QCF3 ,
Zn(Qfur)2(EtOH)2 QPh4F , QPh4Cl , QPh4Br , aac = N-phthaloyl aminoacids) adopt a skewed
octahedral geometry with the butyl groups in trans positions
Fig. 51. Structure of Zn(Qfur )2 (EtOH)2 . (Fig. 60) [100].
Monobutyltin(IV) mixed ligand complexes BuSnCl(Q)(aac) and
BuSn(Q)(aac)2 are six- and seven-coordinate on tin, respectively
(Fig. 60) [101]. A number of penta- and hexacoordinated organ-
charge transfer interactions characterized by long excited-state otin(IV) and tetracoordinated tin(II) complexes (Fig. 61) are active
lifetime [96]. against Musca domestica (house fly), with a higher activity of organ-
A dinuclear complex Al2 (saph)2 (QPh )2 (saph = salicylidene-o- otin(IV) [102].
aminophenol) containing octahedral Al centers (Fig. 57) has been The mono- and dibutyltin(IV) mixed ligand complexes
used to fabricate an OLED (Organic Light-Emitting Diode) device BuSnCl(Q)(␤-dike) and Bu2 Sn(Q)(␤-dike) adopt distorted octahe-
emitting bright green-yellow light [97]. dral geometries in the solid state and solution, while complexes
Mixed ligand octahedral complexes Al(Q)2 (aac) and Al(Q)(aac)2 BuSn(Q)(␤-dike)2 are likely to possess seven-coordinate tin atoms
(Q = QMe , QEt or QPh ; aac = N-phthaloyl aminoacids) (Fig. 58) have (Fig. 62) [103].
been synthesized in 1:1:2 and 1:2:1 molar ratios [98]. In dinuclear complexes Bu2 Sn(Q3Q) and Bu2 Sn(Q4Q) the poly-
Other mixed ligand octahedral complexes Al(Q)2 (␤-dike) and methylene chain length between the two chelating units of the
Al(Q)(␤-dike)2 (Q = QMe , QEt , QPh , or QPh4Cl ; ␤-dike = acetylacetone ligands affect the geometry on the tin atoms, at least in solution:

Me Me
R3 R3
N N
N O N O
R3
O OH2 O O Me
Zn Zn
O
Cl N N N N
N N
C9H19 C9H19
QnPe, R3 = CH2C(CH3)3
QPh4tBu, R3 = C6H4-p-C(CH3)3
C9H19 C9H19 N-N = 4,4'-dinonyl-2,2'-bipyridine
ZnCl(Q)(N-N)(H2O) Zn(Q)2(N-N)

Fig. 52. Structures of ZnCl(Q)(N N)(H2 O) and Zn(Q)2 (N N).

18 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31

Me Me Me Me
Me Me

Me ZnCl(QPh4tBu)(L-L) Me
Me Me
N Me N
N O N O
O O O
Me
Zn Zn
O
L N N Cl L
L L

C16H33O OC16H33
Ph4tBu O O
Zn(Q )2(L-L)
C16H33O OC16H33
O O
C16H33O OC16H33

N N
C16H33O OC16H33
O O
C16H33O OC16H33
O O L-L chelating ligands
C16H33O OC16H33

N N

Fig. 53. Structures of Zn(QPh4tBu )2(L L) and ZnCl(QPh4tBu )(L L).

X Me
H Et Et OH2
O
Et N N N
Me O O N O Zn O
Zn Me O Me Me
N N O O Et O O
Et O O N N N N
Me
Zn
O
X N N N
N
Zn(Q)2(EtOH)2 Zn(QHe)2(EtOH)2

QEt, X = H
QPh3Cl,Et, X= Cl Zn(QEt)2(phen)

Fig. 54. Structures of Zn(Q)2 (H2 O) and of Zn(QEt )2 (phen).

while the solid state structure of complex Bu2 Sn(Q3Q) shows only
the trans-octahedral geometry on tin, in solution two geometri-
cal (trans,trans and cis,cis) isomers have been detected (Fig. 63).
By contrast, the complex Bu2 Sn(Q4Q) exists only in a trans,trans
octahedral geometry, both in the solid state and in solution
(Fig. 63) [10h]. A previously reported analogous binuclear complex
Bu2 Sn(Q2Q) exists in the solid state as the cis,cis-isomer [104].
The steric hindrance on the acyl moiety in Q ligands strongly
affect the geometry in solution of R2 Sn(Q)2 (Q = QCHPh2 , QBn , and
Q1naph ; R = Me, Et, Cy, Bu, tBu, and Ph) [105]. R2 Sn(QCHPh2 )2 (R = Me
and Et) are fluxional, with rapid interconversion between six- and
five-coordinate species, the latter containing a monodentate Q lig-
and. In the solid state the tin atoms are in a skewed trans octahedral
configuration, similar to those in Fig. 61, but the diphenyltin(IV)
complex Ph2 Sn(Q1naph )2 exists in solution as a mixture of trans and
cis isomers [105].
In another series of R2 Sn(Q)2 complexes (Q = QnPe , QiPr , QtBu , QCy ,
QCp , QEtCp , and QMe ; R = Me, Bu, and Ph) the steric bulkiness in the
acyl fragment of QtBu ligand induces fluxionality in solution of the

R3 F
R2 O B
N N O F QMe, R2 = R3 = Me
QPh,Ph,Me, R2 = Ph, R3 = Me
QPh,Ph,Ph, R2 = R3 = Ph
BF2(Q)

Fig. 55. Structure of a ZnO nanoparticle decorated by molecules of QHd ligand. Fig. 56. Structure of BF2 (Q).
 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31 19

Me complex Me2 Sn(QtBu )2 , which exists as an equilibrium mixture of

N six- and five-coordinate tin species [106]. The dialkyltin(IV) com-
N plexes are always trans-octahedral in the solid state, whereas the
diphenyltin(IV) Ph2 Sn(QEtCp )2 shows the two phenyl groups in a
O O
cis arrangement (Fig. 64). DFT studies of this unprecedented cis,
and the corresponding trans configurations, show the former to be
Al O N slightly more stable, in accordance with the diffraction study [106].
O
Mixed ligand complexes Bu2 Sn(Q)(R-benzoate) with fluori-
O nated benzoic acids (Q = QMe , QPh , QPh4F , QPh4Cl , QPh4Br , QPh4I , and
N O Al
QCF3 ; R = 4-F, 2,4-F2 , 3,4-F2 ) are monomeric with the tin atoms in
distorted octahedral geometries environments (Fig. 65), apart the
O O Bu2 Sn(QPh4I )(4-F-benzoate) complex which was found to be dinu-
clear in the solid state, built around an eight-membered Sn2 O4 C2
N macrocycle with one type of six-coordinated tin atom, and the ben-
N zoate ligands bridging the two tin atoms (Fig. 65). These complexes
Me display cytotoxicity against two human cancer cell lines (KB and
Al2(saph)2(QPh)2 Hela) [107].

Fig. 57. Structure of Al2 (saph)2 (QPh )2 .

Me Me
R3 R3
N N
N O N O
R3 O
O O O O
Me
Al Al N
O O
O N N O R O
O O O O
N N
R R R3 = Me, Et, Ph
R = Bn, iPr, iBu
O O
Al(Q)2(aac) Al(Q)(aac)2

Fig. 58. Structures of Al(Q)2 (aac) and Al(Q)(aac)2 .

Me Me
R3 R3 QMe, R3 = Me
N N
QEt, R3= Et
N O N O
Et QPh, R3 = Ph
O O R
O Me O QPh4Cl, R3 = Ph-4-Cl
Al Al
O O
O N N O Me
Me Me
O O
acac, R = Me,
R R bzac, R = Ph

Al(Q)2(β-dike) Al(Q)(β-dike)2

Fig. 59. Structures of Al(Q)2 (␤-dike) and Al(Q)(␤-dike)2 .

Me
Bu R3
O R3 N
O O Me N
Sn O
N O O
O N N O
O R O
Bu Sn N
O
O R O
Bu2Sn(Q)(aac) O O Bu
Cl N R
O R3 CF3 3
Q , R = CF3
O O Me O
N Sn QPh4F, R3 = Ph-4-F BuSn(Q)(aac)2
O O
O R N N QPh4Cl, R3 = Ph-4-Cl
Bu QPh4Br, R3 = Ph-4-Br
R = H, Me, iPr
BuSnCl(Q)(aac) aac = N-phthaloyl aminoacids

Fig. 60. Structures of Bu2 Sn(Q)(aac).

20 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31

N Me
Cl Me
R3 R3 R3 N
O Me Me O O Me
Me Sn Sn R3
O O O O
N N N N N N O
Me Me
Sn O R3
O Me
Me2SnCl(Q) Me2Sn(Q)2 N N

Sn(Q)2
Q = QMe, QPh, QPh4Cl

Fig. 61. Structures of Me2 SnCl(Q), Me2 Sn(Q)2 , and Sn(Q)2 .

Cl Bu Me
R3 R3 R3
R R N
Me O O Me O O
Sn Sn N O Bu
N N O O N N O O
R' R' O R
O
Bu Sn
Bu O
O R'
R'
O
Bu2Sn(Q)(β-dike) Bu2Sn(Q)(β-dike)
R BuSn(Q)(β-dike)2

Q = QMe, QEt, QPh, QPh4Cl,

β-dike: R = R' = Me; R = Me, R' = Ph; R = CF3, R' = Ph; R =CF3, R' = C4H3S

Fig. 62. Structures of BuSnCl(Q)(␤-dike), BuSn(Q)(␤-dike)2 and Bu2 Sn(Q)(␤-dike).

N
N N
N N N
N N O Bu
Bu O O O
Bu Bu Sn Sn
O O O O
Sn Sn O BuO O Bu
O
O Bu O O Bu O
N
N N N N
N N N

trans,trans-[Bu2(Sn(Q3Q)]2 cis,cis-[Bu2(Sn(Q3Q)]2

N N
N N

Bu Bu
O O O O
Sn Sn
O Bu O O Bu O

N N
N N

trans,trans-[Bu2(Sn(Q4Q)]2

Fig. 63. Structures of isomers of Bu2 Sn(Q3Q) and of Bu2 Sn(Q4Q).

Triphenyltin(IV) complexes Ph3 Sn(Q) (Q = Qfur and Qthi ) are
anhydrous compounds while trialkyltin(IV) R3 Sn(Q)(H2 O)n
(Q = Qfur and Qthi ; R = Bu or Me) are always monohydrated [108].
While Ph3 Sn(Q) contain O,O -bidentate Q ligands and tin in
trigonal-bipyramidal environment, in R3 Sn(Q)(H2 O) (R = Bu or Me)
the alkyl groups are in equatorial positions and Q is bonded to tin
only through the ring carbonyl, in trans to water (Fig. 66). Water
is involved in an extended intermolecular H-bonding network
with the chain carbonyl of neighbor molecules. Trialkyltin(IV)
derivatives decompose on heating with release of H2 O and SnMe4
and formation of Me2 Sn(Q)2 [108].
Dihalotin(IV) complexes X2 Sn(Q)2 (Q = QCHPh2 , QBn or Qpy,CF3 ;
X = F, Cl, Br or I) exist as cis isomers in the solid state (Fig. 67),
but isomer conversion was detected in solution and related to the
 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31 21

N Me
Me
N
N
N O O
O
O O Me
Sn Pb O
O
N N O Me
N N

Ph2Sn(QEtCp)2
Pb(QPh)2
Fig. 64. Structure of Ph2 Sn(QEtCp )2 .
Fig. 68. Structure of Pb(QPh )2 .

steric hindrance of the acyl moiety of Q. The complex X2 Sn(Qpy,CF3 )2
contains a N,N -chelating Qpy,CF3 (Fig. 67) [109].
The dichlorotin(IV) complexes display antiproliferative activity
in vitro against three human melanoma cell lines (JR8, SK-MEL-5,
MEL501) and two melanoma cell clones (2/21 and 2/60) [109]. The
activity correlates with the nature of the substituent on position 1
of pyrazole, decreasing in the order pyridyl > Ph  methyl [110].
In the complex Pb(QPh )2 the monomeric units (Fig. 68) are linked
by C H· · ·␲ interaction, intermolecular C H· · ·O hydrogen bonds,
and intermolecular longer secondary Pb· · ·X (X = C or N) interac-
tions, affording two-dimensional layered networks [111].
4.15. Lanthanides
Lanthanide complexes with acylpyrazolone ligands are of par-
ticular interest for their luminescence properties and many studies
deal on their synthesis and emission features. Despite they have
been discussed in several reviews together with Ln complexes of
other ligands [112], to date only one review by Belousov and Droz-
dov was expressly devoted to Ln with acylpyrazolone Q ligands
and to the effect of substituents in the acyl moiety on their struc-
tural and luminescence properties [113]. The Ln(III) chemistry has
been mainly explored, and Ln complexes can be grouped into some
main structural types (Fig. 69): neutral seven-coordinate Ln(Q)3 (L)

Bu Bu F
R3
R O O Me N N O Bu
Sn Sn
O O Me O O I
N N
O
Bu O
I O O Me
Sn
Bu O
Bu2Sn(Q)(benzoate) N N
F Bu
Q = QMe, QPh, QPh4F, QPh4Cl, QPh4Br, QPh4I, QCF3,
R = 4-F, 2,4-F2, 3,4-F2 Ph4I
[Bu2Sn(Q )(4-F-benzoate)]2

Fig. 65. Structures of Bu2 Sn(Q)2 and of dinuclear Bu2 Sn(QPh4I )(4-F-benzoate).

Ph R E
E O
O Qfur, E = O
Me H
Ph Sn O Sn O Qthi, E = S
O Me
N N H N N R = Me or Bu
Ph R R

Ph3Sn(Q) R3Sn(Q)(H2O)

Fig. 66. Structures of Ph3 Sn(Q) and R3 Sn(Q)(H2 O).

Me
R3 O
N F3C
N N
N O
R 3 O N N
O O Sn N O
Me Me
Sn X N CF3
O
X N N X Me
X O
X = F, Cl, Br or I
Q = QCHPh2 or QBn
X2Sn(Q)2 X2Sn(Qpy,CF3)2

Fig. 67. Structures of X2 Sn(Q)2 and X2 Sn(Qpy,CF3 )2 .

22 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31

R2 R2
N N
N R1 N R1
3 3
R R
R3 OO R3 R3 OO R3
O O O O
R2 Ln R2 R2 Ln R2
O O O O
N N N N
N L N N L L N
R1 R1 R1 R1

Ln(Q)3(L) Ln(Q)3(L)2

R2
N
N R1
2 3
R R
N R3 OO R3
N R1 O O
3
R
R3 OO R3 (cation) R2 Ln R2
O O O O
N N
R2 Ln R2 N
OO N
O O
N N R1 R3 R
1
N L L N 1N
R
R1 R1 N R2

Ln(Q)3(L-L) (cation)[Ln(Q)4]

Fig. 69. Structural types of Ln(Q)3 (L), Ln(Q)3 (L)2 , Ln(Q)3 (L L) and (cation)[Ln(Q)4 ].

or eight-coordinated Ln(Q)3 (L)2 or Ln(Q)3 (L L) complexes consti-
tute the most synthesized and investigated structural type, but also
many ionic eight-coordinated (cation)[Ln(Q)4 ] have been reported
and employed in a number of potential applications.
The eight-coordinated Ln complexes generally conforms to a
square antiprism coordination polyhedron, where the possible
ways of ligand arrangement around the central atom in the case
of n = 2 and 0 are reported in Fig. 70a–e.
However, some complexes have been recently found in differ-
ent geometries, such as a bicapped trigonal prismatic polyhedron
(Fig. 71a and b) or even with a dodecahedral geometry on the Ln
center (Fig. 71c).
Many novel Ln complexes have been reported after 2004, giv-
ing impressive advancement on the knowledge of their emission
O O
O L O O
O L O L
O O L O
O O
(a) (b)
properties, and some heteronuclear complexes with d–f metal have
also been synthesized.
Complexes Eu(Q)3 (H2 O)2 and Eu(Q)3 (TPPO)(H2 O) (Q = Q1naph ,
Q Ph4NMe2 and QPh4CN ) contain electron-poor or electron-rich aryl
substituents in the 4-acyl moiety Q, which alter the triplet state
energy, affecting the quantum yield of Eu emission and also the
energy transfer efficiency from the ligand to Eu [10i]. The complex
Eu(Q1naph )3 (TPPO)(H2 O) contains a distorted bicapped trigonal
prismatic coordination geometry on the metal center [10i].
The Tb and Gd complexes Ln(QiPr )3 (H2 O)2 and
Ln(QiPr )3 (pyphenCN), (Ln = Tb and Gd; pyphenCN = pyrazino[2,3-
f][1,10]phenanthroline-2,3-dicarbonitrile) (Fig. 72) are in a
distorted bicapped-trigonal prismatic geometry [114]. The flu-
orescent quantum yield of Tb(QiPr )3 (pyphenCN) is lower than
that of Tb(QiPr )3 (H2 O)2 , because the triplet energy level of the
chelating pyphenCN is a bit higher than that of 5 D4 of Tb3+ and
lower than that of QiPr , resulting in a back energy transfer from Tb
O
O O to pyphenCN [114]. The emission features of Tb(QiPr )3 (pyphenCN)
depend significantly on the nature of the anions added into the
L L solution: (1) by addition of fluoride (or acetate) anions into the
acetonitrile solution of Tb(QiPr )3 (pyphenCN), the replacement
O O of pyphenCN with fluoride (or acetate) anions takes place, the
O above back-energy transfer prohibited and the fluorescence of the
terbium complex enhanced; (2) after addition of excess fluoride (or
(c) acetate) anions, the replacement of QiPr with fluoride (or acetate)
anions does not allow the ligand QiPr sensitized energy transfer of

O O
O O O O
O O O O O
L O O O
O L
L O O O
O O O O O L O L O
L O L O O O
O O
(d) (e) L O
(a) (b) (c)
Fig. 70. Square antiprismatic polyhedra for Ln(Q)3 (L)2 , Ln(Q)3 (L L) and
(cation)[Ln(Q)4 ]. Fig. 71. Bicapped trigonal prismatic and dodecahedral polyhedra for Ln(Q)3 (L)2 .
 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31 23

Me Me
Me Me

Me O OH2 Me O N N CN
N Ln N Ln
O N O
N OH2 N N CN

Ln = Tb and Gd 3
3

Ln(QiPr)3(H2O)2 Ln(QiPr)3(pyphenCN)

Fig. 72. Structures of Ln(QiPr )3 (H2 O)2 and Ln(QiPr )3 (pyphenCN).

Me
N
N Ph
AD
AD OO AD Me
O O
Me O
[H3O]+ Me Ln Me N
O O N Ln
N N N O
N N
OO N
Ph Ph Ln = Tb and Eu
AD Me
Ph N
N Me AD = 3

[H3O][Ln(QAD)4] Ln(QAD)3(4,4'-Me2bipy)2

Fig. 73. Structures of [H3 O][Tb(QAD )4 ] and Tb(QAD )3 (4,4 -Me2 bipy).

the terbium complex, with a fluorescence quenching of the system In Tb-cored dendritic complexes Tb(QGn )3 (L)m (n = 0, m = 2,
[114]. L = H2 O and EtOH, n = 1, m = 2, L = H2 O, n = 2, m = 1, L = H2 O, n = 3,
In the complex Tb(QPh )3 (H2 O)2 the intermolecular energy losses m = 0) the coordination numbers shift from eight to six by increas-
were avoided by sorbing the complex on a polymer matrix PMMA ing the dendritic hindrance of the QGn ligands, with progressive
(polymethylmethacrylate). As a result, the luminescence intensity esclusion of the solvent molecules. For n = 0 and 1 the Tb exists in
of the complex Tb(QPh )3 (H2 O)2 increased [115]. a dodecahedral geometry (Fig. 75) [18].
Complexes Ln(QAD )3 (EtOH)(H2 O) (Ln = Tb, Eu; HQAD = 1-phenyl- They exhibit high stability and the luminescence quantum yield
3-methyl-4-adamantylcarbonyl-pyrazol-5-one), [H3 O][Tb(QAD )4 ], increases by increasing the dendritic generation from n = 0 to n = 3.
Ln(QAD )3 (N–N) (Ln = Tb, Eu; N–N = 1,10-phenanthroline (phen), The investigation of the triplet state and oxygen quenching con-
2,2 -bipyridyne (bipy), and 4,4 -dimethyl-2,20-bipyridyne (4,4 - firmed that this enhancement of the energy transfer is attributed
Me2 bipy)) are luminescent, and the crystal structures of to both an “antenna effect” and a “shell effect” [18].
[H3 O][Tb(QAD )4 ] and Tb(QAD )3 (4,4 -Me2 bipy) show the Tb ions in A study on the synergistic solvent extraction of sev-
a square antiprismatic environment, the H3 O+ cation in the former eral Ln ions (La3+ , Nd3+ , Eu3+ , Ho3+ and Lu3+ ) with HQPh
complex being stabilized by H-bonding (Fig. 73) [10j]. and the calix[4]arene 5,11,17,23-tert-butyl-25,26,27,28-
The anionic complex [H5 O2 ][Eu(QCy )4 ] containing the Zundel tetrakis(dimethylphosphinoylmethoxy), in CHCl3 showed that
ion H5 O2 + and the QCy ligans (Fig. 74) possesses high thermal sta- the Ln are extracted in the form of Ln(QPh )3 (calix[4]arene) [117].
bility and luminescent emission. It is ionic in acetone and ethanol The stoichiometry and the structure of the solid complexes were
solution and the Zundel cation is stabilized by strong hydrogen proposed as [Eu(QPh )2 (calix[4]arene)](Cl) Figure (Fig. 76). The
bonding with the N atoms of the anionic QCy ligand [116]. authors suggested that the different composition of the mixed
complex in solution and in solid state is a result of the different
experimental conditions.
A series of Ln complexes Ln(QEt )3 (H2 O)2 ·2EtOH (Ln = Nd, Sm,
Me
N Gd, and Dy) were synthesized by the hydrothermal method with
N Ph the starting ligand 1-phenyl-3-methyl-4-(salicylidene hydrazone)-
propionyl-5-pyrazolone changed into QEt during the formation of
OO
H H O O complexes [118].
O
Me Eu Me Anionic complexes [L][Ln(QPh )4 ] containing a positively charged
H
O O hemicyanine chromophore with a long alkyl chain (Ln = Nd, Er,
O
H H N
N N
N Yb; L = (E)-N-hexadecyl-N ,N -dimethylamino-stilbazolium) show
OO
near-infrared luminescence decay times comparable to the better
Ph Ph
behaving Ln complexes in solution [119].
Ph N A new dysprosium complex Dy(QiPr )3 (TPPO)2
N Me
(TPPO = triphenylphosphine oxide) shows a distorted bicapped
trigonal prismatic environment on the metal center [120] and,
[H5O2][Eu(QCy)4] based on its photophysical properties, it was used to fabricate a
series of electroluminescent devices [121]. A similar samarium
Fig. 74. Structure of [H5 O2 ][Eu(QCy )4 ].
24 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31

O EtOH O
O OH2
Tb Tb
O OH2 O OH2
N N
N N

3 3

Tb(QG0)3(EtOH)(H2O) Tb(QG1)3(H2O)2
G0 G1

Fig. 75. Structures of Tb(QG0 )3 (EtOH)(H2 O) and Tb(QG1 )3 (H2 O)2 .

complexes have low transition temperatures and low viscos-

Me N ity mesophases and their thermal and photophysical properties
N
Me
P O
O O Me
O Me
O Cl-
Eu O P Me
O Me O
O P
O Me
Me O P Me O
N N Me
[Eu(QPh)2(calix[4]arene)](Cl)
Fig. 76. Structure of [Eu(QPh )2 (calix[4]arene)](Cl).
complex Sm(QiPr )3 (TPPO)2 displays high luminescence, including
highly efficient transfer of electronic excitation from the ligand-to-
metal ion center and sufficient protection of the samarium center
against nonradiative deactivation from the environment [122].
With analogous erbium complex Er(QiPr )3 (TPPO)2 a multilayer
phosphorescent organic light emitting diode was fabricated [123].
The complex Tb(QiPr )3 (DPPOC) (DPPOC = 9-(4-tert-
butylphenyl)-3,6-bis(diphenylphosphineoxide)-carbazole) was
incorporated in the emission layer of a was prepared by vacuum
co-deposition of a previously reported complex Tb(QiPr )3 (H2 O)2
[125] and DPPOC in molar ratio = 1:1. The electroluminescent (EL)
device demonstrates pure emission from terbium centers, even at
the highest current density [124].
The complex Er(QiPr )3 (TPPO) contains a seven-coordinate Er in
a distorted monocapped trigonal prism and displays an efficient
near-infrared (NIR) luminescence [126].
A “building blocks” strategy has been used for the synthesis
of luminescent coordination polymers Ln(Q)3 (dppxO2 ) (Ln = Eu, Tb
or Gd; Q = Qthi and QCp ; dppxO2 = bis(diphenylphosphine)methane
dioxide – dppmO2 , bis(diphenylphosphine)ethane dioxide –
dppeO2 , and bis(diphenylphosphine)butane dioxide – dppbO2 )
[127]. {Ln(Q)3 } mononuclear fragments have been linked by
dppxO2 bridges (dppxO2 = dppeO2 or dppbO2 ) affording coordina-
tion polymers, while monomeric species have been isolated with
dppmO2 (Fig. 77) [127].
The liquid-crystalline columnar ligand L (L = 4,7-bis[3,4,5-(tri-
hexadecyloxy)benzoyloxy-methyl]-1,10-phenanthroline) (Fig. 53)
has been used to induce low temperature mesomorphism in his
complexes Ln(QPh )(L): stable liquid crystalline Eu(III) and Tb(III)
depend on their different solid, soft and liquid crystalline organi-
zations [128].
The complexes Ln(QMe )3 (H2 O)2 ·MeCOOEt (Ln = Tb and Eu)
are isostructural with two independent, but structurally similar,
molecules in the structural unit, one conforming to a distorted
square antiprism geometry and the other to a bicapped trigonal-
prism [129]. The Tb(III) complex displays intensely green emission
of Tb(III)-centered, while the Eu(III) complex does not emit red
luminescence [129].
The obtainment of anhydrous Ln complexes has been faced by
Bochkarev, who succeeded in the preparation of novel Ln(QiPr )3
(Ln = Y, Nd, Gd, Tb, Er, Tm, Lu) in high yields by the reaction of HQiPr
with Ln metals in the form of filings in thf solution of I2 , in order to
produce catalytic amounts of LnI3 [130]. The isolated compounds
were found to sublime in vacuum. The sublimed complexes exist
as dimeric species [Ln(QiPr )3 ]2 in which the metals are bridged by
two QiPr ligands and their coordination environment is a distorted
monocapped trigonal prism (Fig. 78).
Other anhydrous dinuclear Ln complexes [Ln(QtBu )3 ]2 (Ln = Pr,
Nd, Gd, Tb, Tm, and Lu) were synthesized by the same proto-
col giving almost quantitative yields [131]. During sublimation of
[Ln(QtBu )3 ]2 (Ln = Y, Ho, Er, Tm, and Lu) the gas phase contains only
monomeric species [132,133].
The Gd(Q)3 complexes (Q = QPh,py,Ph , QPh,thi,Ph ) was reported to
compare their phosphorescence with that of Ln(L)3 complexes
(Ln = Tb and Gd) containing tripodal Schiff bases L prepared by
reaction of HQ with tris(2-aminoethyl)amine: the new Schiff base
ligands have relatively high located triplet energy levels in com-
parison with their simple Q analogs and act as efficient “antenna”
sensitizers for the green photoluminescence of Tb3+ ion [134].
The complex Tb(QpyCOOH )3 (H2 O)2 with a tridentate acylpyrazolone
HQpyCOOH (Fig. 79) displasy a strong luminescence and interacts
with albumin (BSA) through van der Waals interactions and hydro-
gen bonds [135].
Two ytterbium complexes Yb(QPh4tBu )3 (batophen)2 (batophen =
bathophenanthroline, or 4,7-diphenyl-1,10-phenanthroline) and
Yb(QiPr )3 (TPPO)2 , possessing near-infrared electroluminescence,
were incorporated in double-emission-layers devices [136]. An
anhydrous Tb(QiPr )3 was obtained by reaction of terbium tert-
butoxide with HQiPr and was used in reaction with copolymers
containing carbazole and terpyridine fragments in side chains,
to afford photo- and electroluminescence polymeric materials
(Fig. 80) [137].
Analogous photoluminescence terbium-containing copolymers
have been prepared by ring-opening metathesis copolymerization
 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31 25

O O
Me N O
N O Ln = Eu, Q = Qthi, X = E, n = 2
Ph Ln Ln = Eu, Q = Qthi, X = B, n = 4
Ph
R3 P O Ln = Tb, Q = Qthi, X = E, n = 2
R3
O
(CH2)n O O
O O Ln = Tb, Q = Qthi, X = B, n = 4
O O P Ph Ln = Eu, Q = QCp, X = E, n = 2
Me Ph
Ln Ln = Eu, Q = QCp, X = B, n = 4
O O R3 Ln = Tb, Q = QCp, X = E, n = 2
N
N Ln = Tb, Q = QCp, X = B, n = 4
O O
Ph
P Ph N Me Ln = Gd, Q = Qthi, X = E, n = 2
N Ln = Gd, Q = Qthi, X = B, n = 4
Ph (CH2)n Ph Ph
Ph P Ln = Gd, Q = QCp, X = E, n = 2
Ln = Gd, Q = QCp, X = B, n = 4
O O
O O
Ln Me N
O N
O
O
O
R3 O
Ln = Eu, Q = Qthi R3 O R3
Ln = Tb, Q = Qthi O O
Me Me
Ln = Eu, Q = QCp Ln
Ln = Tb, Q = QCp O O
N O N
Ln = Gd, Q = Qthi N N
O
Ln = Gd, Q = QCp Ph P Ph Ph
P Ph
Ph
Ph

Fig. 77. Structures of mono- and polynuclear Ln(Q)3 (L).

Me Me
Me
N
N Me Ph N O O
Me
N O O
Ph O O O Me O
O N N
Me O O
Me O O
Me O Ln Ln O Me O O
Me O Me
N N O O O O
Me O Ph
Ph N O
Me N Me
N N
Me Me Me
iPr Ln = Y, Nd, Gd, Tb, Er, Tm and Lu
[Ln(Q )3]2

Fig. 78. Structure of dimeric [Ln(QiPr )3 ]2 .

*
m n

O C O
O
HO N
O

N N
OH2 N N
Tb
O OH2 Tb
Me
O O O
N
N
N
N
3 Me 3

Tb(QpyCOOH)3(H2O)2 carbazole-containing Tb(QiPr)3 copolymer

Fig. 79. Structure of Tb(QpyCOOH )3 (H2 O)2 . Fig. 80. Structure of terbium-containing polymeric material.
26 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31

Me N
Me
N H N N
N Ph N
Ph H
O O O OH
O 2
O O O Ln
HO OH EtOH
H O Ln O N
Ln OO O
Me O O Me
N N HO O O H NN N
O O Ph N
H N
N Ph H N
N
Me Me
Fig. 83. Structure of Ln(QHd )3 (H2 O)(EtOH).
H H
[La2(μ-Q )3(Q )3(H2O)3]·2MeOH

Fig. 81. Structure of [La2 (␮-QH )3 (QH )3 (H2 O)3 ]·2MeOH.

Me S S Me
N
N N
R3 N O O
Et O
O
Me O Cl Cl
O H Ce
Ln Ln = Eu and Sm; Q = Qthi Cl
N O O O
N O Me Ln = Tb and Dy, Q = QnPe O N
P O O
N
O S
O Me N S Me
3 Me N Cl
Me O

Ln(Q)3(LP)(EtOH) Ce(QPh4Cl,thi).3(toluene)

Fig. 84. Structure of Ce(QPh4Cl,thi )·3(toluene).

Fig. 82. Structure of Ln(Q)3 (LP)(EtOH).

(ROMP) of the complex Tb(QiPr )2 (Qnorb )(TPPO)2 and carbazole- ligand-to-metal energy transfer. The Tb complex exhibits a green
containing norbornene comonomers [138]. luminescence both in the solid state and solution, with an evident
Ln complexes Ln(QH )3 ·nSolv (Ln = La, Nd, Sm, Eu, Gd, Tb, Dy, “antenna” effect [143].
and Yb; Solv = H2 O or EtOH) can be grouped into two series, one The complexes Ln(QHd )3 (H2 O)(EtOH) (Ln = Eu, Gd, and Tb) have
with lanthanum and neodymium, and the other with samarium, been obtained with the long aliphatic chain QHd , their structure
europium, gadolinium, terbium, dysprosium, and ytterbium [139]. showing the three aliphatic fragments n-C16 H33 codirected, with
The structure of lanthanum complex is dinuclear with composition formation of layers bound in accordance with the fastener-sticker
[La2 (␮-QH )3 (QH )3 (H2 O)3 ]·2MeOH, where the La atoms are struc- principle (Fig. 83) [144]. The Tb complex is luminescent at room
turally nonequivalent and bridged by three QH ligands (Fig. 81) temperature, while luminescence of Eu complex is very low at room
[139]. temperature but increases intensely on cooling, a feature that could
Anionic complexes Na[Ln(QH )4 ]·2H2 O and [NBu4 ][Ln(QH )4 ] be useful for “luminescent thermometers” [144].
(Ln = Nd, Sm, Eu, and Tb) conform to a square antiprismatic coordi- The new ligand HQF5Ph (1-phenyl-3-methyl-4-(2,3,4,5,6-
nation polyhedron [140]. Sodium cations in Na[Ln(QH )4 ]·2H2 O are pentafluorobenzoyl)-pyrazole-5-one) has been reacted with
connected to nitrogen atoms of QH , affording two interpenetrat- lanthanide silylamides Ln[N(Me3 Si)2 ]3 affording complexes
ing three-dimensional frameworks that combine discrete complex Ln(QF5Ph )3 (thf) (Ln = Sm, Eu, Gd, Tb, Lu) and, in the presence of
anions with Na+ cations [140]. The solid Nd(III), Sm(III) and Tb(III) TPPO, also Ln(QF5Ph )3 (TPPO)2 ·xEtOH, which are luminescent at
complexes are able to afford intense luminescence. The hydro- room temperature [145].
nium complexes [H3 O][Ln(QH )4 ]·nH2 O (Ln = Nd, Sm, Eu, and Tb; The complex Ce(QPh4Cl,thi ). 3(toluene) with cerium in +4 oxida-
n = 1–3) are isostructural and contain the [Ln(QH )4 ]− anions with tion state contains eight-coordinated cerium atom in a distorted
the metal in a distorted tetragonal antiprismatic environment and triangular dodecahedral coordination geometry, and the complex
the anionic complexes are linked by H-bonding with the hydrox- is also involved in a 3D network through weak intermolecular ␲· · ·␲
onium counter-ion and water molecules [141]. The Tb(III) and and C-H· · ·␲ interactions (Fig. 84) [146].
Sm(III) complexes show strong luminescence in the solid state,
in particular [H3 O][Tb(QH )4 ]·H2 O affords high efficiency lumines-
cence and high luminescence quantum yield [141]. The complexes Me
Me E
Ln(QH )3 (phen) (Ln = Nd, Sm, Eu, Gd, Tb, Dy, and Yb) exist with a
distorted square antiprismatic geometry on Ln and are solid state Me N
O
emitters [142]. N N
Drozdov has recently reported mixed ligand complexes N Nd Ir E
N O N N
Ln(Q)3 (LP)(EtOH) (Ln = Eu, Sm, Tb and Dy, Q = QnPe and Qthi , N
LP = ethyl(diethoxyphosphoryl) acetate) contains the Ln atom in a
distorted square antiprismatic environment (Fig. 82) [143]. F E = H or F
The Sm and Eu complexes exhibit orange and red luminescence, 3 E
E
respectively, only on cooling to the temperature of liquid N2 . The Ir-Nd-bimetallic complexes
Dy complex emits in the blue-green range, the most intense band
being likely due to the emission of the ligand, with no detectable Fig. 85. Structure of Ir–Nd bimetallic complexes.
 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31 27

Me Me
N N
N (CH2)8 N

O O O O
3
Ln Ln
Ln = Tb and Gd
OH2 OH2

Ln2(Q8Q)3(H2O)2

Me Me
N N
N (CH2)8
OH2 N
O O O O O
O O
Tb
Na
O O O O O O
O N
N (CH2)8
N N
Me Me

[Na(DB18C6)(H2O)]]Tb2(Q8Q)4]

Fig. 86. Structures of Ln2 (Q8Q)3 (H2 O)2 , and [Na(DB18C6)(H2 O)]]Tb2 (Q8Q)4 ].

*
N N *
O Et N
N Et Et
O O O O O
O H2O
O O O Et
H2O Ln Ln OH2 Ln = Tb and Eu
N
Et O O
O N N O
O OH2 N N O
O
N
Et O
* N N
N
n
*

[Ln2(Q3py3Q)3(H2O)4]n

Fig. 87. Structure of [Ln2 (Q3py3Q)3 (H2 O)4 ]n .

In the chapter 4.9 dedicated to group 9 metals, we have The complexes Tb2 (Q8Q)3 (H2 O)2 , Gd2 (Q8Q)3 (H2 O)2 , and
mentioned Ir(Qpy,R3 )(dfppy)2 complexes (R3 = CF3 , Ph, Bn, Ph4F, [Na(DB18C6)(H2 O)]]Tb2 (Q8Q)4 ] (DB18C6 = dibenzo-18-crown-
2naph; dfppy = 2,4-difluoro)phenylpyridine) used to prepare Ir-Eu 6) were reported and the latter contains a terbium center
bimetallic derivatives, where the bridging Qpy,R3 ligands are bonded coordinated by two tetradentate bis(acylpyrazolone) ligands in
to iridium through the N,N -chelating face and to europium through
the O,O -chelating face (Fig. 37) [15]. Additional hetererobimetallic
Ir-Ln complexes have been obtained by reaction of Nd(QiPr )3 (H2 O)2
L
and octahedral Ir(III) complexes containing a potentially bridging
5-fluoro-2-(pyrimidin-2-yl)-1H-benzo[d]imidazole (Fig. 85) [147].
The iridium complexes have suitable triplet energy levels for sensi- Tb
tizing Nd3+ , affording an efficient energy transfer from Ir moiety to
Nd both in solutions and in films. Non-doped OLEDs were fabricated
by using co-deposition film of Ir–Nd assemblies as the emitting
layer and such electroluminecsnt devices exhibit a NIR emission L = H2O or DMF
Tb
from Nd centers.
The nitrosopyrazolone shown in Fig. 32 and its perfluorinated
analog, prepared by 1-pentafluorophenyl-3-methyl-5-pyrazolone L
and isoamylnitrite, afforded Er and Yb complexes displaying NIR
emission with long lifetimes [148].
Tb2(Q2Q)3(L)2
Since 2005, some papers appeared on the use of
bis(acylpyrazolone) ligands with lanthanide acceptors. Fig. 88. Structure of Tb2 (Q2Q)3 (H2 O)2 and Tb2 (Q2Q)3 (dmf)2 .
28 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31

Ph
Ph
P O *
Ph
Ph
P O Tb Tb O P
Ph
Ph
* Tb Tb O P
Ph
Ph

n
[Tb2(Q2Q)3(dppeO2)]n

Fig. 89. Structure of polynuclear [Tb2 (Q2Q)3 (dppeO2 )]n .

a distorted square antiprismatic environment, while the sodium 4.16. Actinides

coordination sphere is a distorted hexagonal pyramid involving
six O atoms of the crown ether DB18C6 and one water molecule Thorium(IV) quadruple-stranded helical complexes, with for-
(Fig. 86) [149]. mula Th2 (Q3Q)4 (DMF)2 and Th2 (Q4Q)4 (DMF)2 , contain two capped
The terbium complex emits bright-green luminescence with square-antiprismatic nine-coordinated Th centers, with four
high quantum yield and, due to the large overlap of the emission bis(acylpyrazolone) chelating ligands and two DMF molecules in
bands of the crown ether ligand with those of the Q8Q, there is an the apical positions (Fig. 90) [152].
energy transfer from the crown ether to the metal center through The complex UO2 (QPh4NO2 )2 (H2 O) contains a seven-coordinated
the triplet state of the Q8Q ligand [149]. uranium [61]. The complexes UO2 (QPh )2 (DRDPU). 0.5(solvent)
A novel proligand H2 Q3py3Q, containing a bridging pyridine (DPDPU = N,N -dipropyl-N,N -diphenylurea, solvent = p-xylene
ring between the chelating moieties, afforded polynuclear com- [153]; DEDPU = N,N -diethyl-N,N -diphenylurea, solvent = toluene
plexes [Ln2 (Q3py3Q)3 (H2 O)4 ]n (Ln, Eu and Tb) (Fig. 87) emitting [154]) both contain seven-coordinated uranium centers with two
the characteristic photoluminescence with high intensity, narrow oxo ligands in trans positions of a distorted pentagonal bipyramidal
half-peak width, and monochromatic light [150]. geometry (Fig. 91).
Dinuclear terbium complexes Tb2 (Q2Q)3 (H2 O)2 and
Tb2 (Q2Q)3 (DMF)2 , having a triple-stranded helical structure thanks
Me
to the bis(acylpyrazolone) ligand Q2Q, contain seven-coordinated
terbium atoms (Fig. 88) [151]. N
By slow substitution of DMF molecules in Tb2 (Q2Q)3 (DMF)2 N
R
by dppeO2 , the polynuclear [Tb2 (Q2Q)3 (dppeO2 )]n is obtained, its O
O
crystal structure consisting in infinite parallel chains formed by the O
O
helical units {Tb2 (Q2Q)3 } bridged by dppeO2 ligands (Fig. 89). Two U
O
types of chains have been found, corresponding to the two differ- R O
O
ent optical isomers of the helix (left and right-handed, respectively)
[151]. R = Et or Pr N
These complexes show intense metal-centered green lumines- N
cence due to ligand-to-metal energy transfer and high quantum Me
yield in ethanol solution [151].
UO2(QPh)2(DRDPU)

Fig. 91. Structure of UO2 (QPh )2 (DRDPU). 0.5(solvent).

Me N
N
dmf
Me O
Th O O

N O U O
O S N
O O
N S O O
O U N

O O O
Th Me

dmf N
N Me

Th2(Q4Q)4(DMF)2 [{UO2(QPh)2}2(DBSOB)]

Fig. 90. Structure of Th2 (Q4Q)4 (DMF)2 . Fig. 92. Structure of [{UO2 (QPh )2 }2 (DBSOB)].
 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31
The dinuclear U(IV) complex [{UO2 (QPh )2 }2 (DBSOB)]
(DBSOB = 1,4-di(butylsulfinyl)butane) reveals two {UO2 (QPh )2 }
moieties conforming to distorted pentagonal bipyramid geome-
tries on each uranium atom, and the two {UO2 (QPh )2 } connected
by a bridging DBSOB ligand (Fig. 92) [155].
The crystal structure of solvated complex
UO2 (QPh)2 (EtOH)]·EtOH consists of two chelating QPh ligands
and the ethanol molecule in the equatorial plane of a pentagonal
bipyramid, the axial positions of uranium being occupied by the
two oxo ligands [156].
5. Conclusion and perspective
The acylpyrazolones ligands have shown to possess structural
and electronic features for a versatile coordination chemistry,
which has rapidly grown in the last decade and expanded to metal-
lic elements previously underestimated. The versatility of these
molecules as ligands derives mainly from the easy functionalization
on the C4 carbon of pyrazolone ring with different acyl moieties (R3
in Fig. 1) that can vary in complexity. However, also the substitution
in R1 position of the pyrazolone have allowed to obtain ligands with
completely different coordinating abilities, as in the case of Qpy,R3
ligands incorporating a pyridine in R1 , which are suitable bridg-
ing ligand affording heterobimetallic Ir-Eu, Ir-Nd, Cu-Zn and Cu-Ru
complexes, and useful to prepare Ag(I), Cu(I), Ir(III), Pt(II), and Ru(II)
complexes with N-bonded Qpy,R3 ligands.
Less investigated was instead the substitution in R2 position,
i.e. in C3 of the pyrazolone (see Fig. 1), even if some fascinat-
ing examples of dendritic terbium complexes have demonstrated
such possibility. It is well known that the presence of the pyrazole
ring stabilizes the metal derivatives by facilitating an extensive ␲-
conjugate system, when the heterocyclic ring is directly bonded
to an aromatic substituent. Such conjugation has been improved
by the introduction of groups such as 1- and 2-naphthoyl and 4-
biphenyl. However, also the introduction of partially unsaturated
moieties, such as norbornene, gave the possibility to incorporate
such ligands into copolymers with interesting catalytic features.
Moreover, the functionalization of Q ligands with long aliphatic
chain has given the possibility to modulate and improve van der
Waals interactions between the metal complexes and hydrophobic
surfaces, for the preparation of composite functional materi-
als.
The biological properties of the pyrazolone moiety have led
to the employment of Q ligands for the synthesis of metal com-
plexes with potential antitumor and antimicrobial activity, with
some remarkable results mainly with Ti(IV), Cu(II), Sn(IV), Pt(II)
and Ru(II). However it is mainly in the coordination chemistry of
lanthanides that many efforts have been made to design Q ligands
with well suited substituents, in order to finely tune the electronic
and steric features of the ligand and to modulate the optical prop-
erties of the metal complexes. Based on the large number of studies
on Ln(III) acylpyrazolone complexes, some general rules can be
delineated to increase the luminescence intensity, by changing the
substituent in the acyl moiety: (a) in the case of Tb(III) complexes,
aliphatic substituents are more convenient to produce an elevated
triplet energy level of the Q ligand; (b) by contrast, in the case of
Eu(III) and Sm(III) complexes, a better choice is the introduction of
aromatic and conjugated unsaturated groups in the acyl moiety.
Less explored are the potentials of metal acylpyrazolonates in
catalysis, even if some work on V(IV) and Mo(VI) have recently
opened this pathway. The asymmetrical O,O -chelating face of
the acylpyrazolones, with the different donating ability of the
CO(chain) with respect to CO(pyrazole) arms, could let to novel cat-
alytic properties of metal and organometal complexes, particularly
among transition elements.
29
The construction of potentially tetradentate Q(spacer)Q ligands
has led to some interesting metal complexes with different prop-
erties, partly related to the presence of two chelating moieties
differently connected to each other through rigid aromatic spac-
ers or flexible aliphatic, where the latter were shown suitable to
attain triple- or quadruple-stranded helical structures for Ln and Ac
dinuclear complexes. They can be view as secondary building units
for the construction of supramolecular networks with 1D polynu-
clear coordination complexes.
However, the coordination chemistry of several metals is again
waiting to be explored with acylpyrazolone ligands and to display
its potentials, as for example with Zr, Hf, Nb, Ta, W, Re, Os, Pd, Au
and even Fe. In summary, we can expected that the field of acylpyra-
zolone ligands and their metal complexes will maintain a high level
of interest in the near future.
Acknowledgement
University of Camerino is gratefully acknowledged.
References
[1] L. Claisen, E.F. Ehrhardt, Chem. Ber. 22 (1889) 1009.
[2] (a) A.R. Siedle, in: G. Wilkinson, R.D. Gillard, J.A. McCleverty (Eds.), Compre-
hensive Coordination Chemistry, Pergamon, Oxford, UK, 1987, pp. 365–412;
(b) C. Pettinari, F. Marchetti, A. Drozdov, in: J.A. McCleverty, T.J. Meyer
(Eds.), Comprehensive Coordination Chemistry II, Elsevier, Amsterdam, The
Netherlands, 2004, pp. 97–115, chapter 1.6.
[3] (a) F. Stoltz, J. Prakt. Chem. 55 (1897) 145;
(b) A. Michaelis, F. Engelhardt, Ber. Dtsch. Chem. Ges. 41 (1908) 2668;
(c) W. Wislicenus, H. Elvert, P. Kurtz, Ber. Dtsch. Chem. Ges. 46 (1913) 3395.
[4] B.S. Jensen, Acta Chem. Scand. 13 (1959) 1668.
[5] Y.A. Zolotov, N.M. Kuzmin, Extraction of Metals by Acylpyrazolones, Nauka,
Moscow, Russia, 1977.
[6] (a) A.K. Gadad, B.S. Kittur, S.G. Kapsi, C.S. Mahajanshetti, S.B. Rajur, Arzneim.
Forsch. 46 (1996) 1082;
(b) T.D. Penning, J.J. Talley, S.R. Bertenshaw, J.S. Carter, P.W. Collins, S. Docter,
M.J. Graneto, L.F. Lee, J.W. Malecha, J.M. Miyashiro, R.S. Rogers, D.J. Rogier, S.S.
Yu, G.D. Anderson, E.G. Burton, J.N. Cogburn, S.A. Gregory, C.M. Koboldt, W.E.
Perkins, K. Seibert, A.W. Veenhuizen, Y.Y. Zhang, P.C. Isakson, J. Med. Chem.
40 (1997) 1347.
[7] F. Marchetti, C. Pettinari, R. Pettinari, Coord. Chem. Rev. 249 (2005) 2909.
[8] J.S. Casas, M.S. García-Tasende, A. Sánchez, J. Sordo, Á. Touceda, Coord. Chem.
Rev. 251 (2007) 1561.
[9] W. Holzer, K. Mereiter, B. Plagens, Heterocycles 50 (1999) 799.
[10] (a) A.B. Uzoukwu, S.S. Al-Juaid, P.B. Hitchcock, J.D. Smith, Polyhedron 12
(1993) 2719;
(b) Y. Akama, M. Shiro, T. Ueda, M. Kajitani, Acta Crystallogr. Sect. C 51 (1310)
(1995);
(c) J.A.M. Guard, P.J. Steel, Aust. J. Chem. 47 (1994) 1453;
(d) A. Cingolani, E. Effendy, F. Marchetti, C. Pettinari, R. Pettinari, B.W. Skelton,
A.H. White, Inorg. Chem. 41 (2002) 1151;
(e) A. Cingolani, F. Marchetti, C. Pettinari, R. Pettinari, B.W. Skelton, A.H. White,
Inorg. Chem. Commun. 7 (2004) 235;
(f) E. Effendy, F. Marchetti, A. Marinelli, C. Pettinari, B.W. Skelton, A.H. White,
Inorg. Chim. Acta 366 (2011) 388;
(g) P.N. Remya, C.H. Suresh, M.L.P. Reddy, Polyhedron 26 (2007) 5016;
(h) F. Effendy, A. Marchetti, C. Marinelli, B.W. Pettinari, A.H. Skelton, White,
Inorg. Chim. Acta 366 (2011) 388;
(i) M. Shi, F. Li, T. Yi, D. Zhang, H. Hu, C. Huang, Inorg. Chem. 44 (2005) 8929;
(j) C. Pettinari, F. Marchetti, R. Pettinari, P. Natanti, A. Drozdov, S. Semenov,
S.I. Troyanov, V. Zolin, Inorg. Chim. Acta 359 (2006) 4063.
[11] (a) M.J. O’Connell, C.G. Ramsay, P.J. Steel, Aust. J. Chem. 38 (401) (1985).
[12] F. Marchetti, J. Palmucci, C. Pettinari, R. Pettinari, F. Condello, S. Ferraro, M.
Marangoni, A. Crispini, S. Scuri, I. Grappasonni, M. Cocchioni, M. Nabissi, M.R.
Chierotti, R. Gobetto, Chem. Eur. J. 21 (2015) 836.
[13] V.B. Kurteva, M.A. Petrova, J. Chem. Educ. 92 (2015) 382.
[14] A. Cingolani, E. Effendy, F. Marchetti, C. Pettinari, R. Pettinari, B.W. Skelton,
A.H. White, Inorg. Chem. 43 (2004) 4387.
[15] W. Jiang, B. Lou, J. Wang, H. Lv, Z. Bian, C. Huang, Dalton Trans. 40 (2011)
11410.
[16] D.J. Wallace, J.M. Straley, J. Org. Chem. 26 (1961) 3825.
[17] B.T. Thaker, K.R. Surati, C.K. Modi, Russ. J. Coord. Chem. 34 (2008) 25.
[18] L. Shen, M. Shi, F. Li, D. Zhang, X. Li, E. Shi, T. Yi, Y. Du, C. Huang, Inorg. Chem.
45 (2006) 6188.
[19] E. Budzisz, M. Malecka, B.K. Keppler, V.B. Arion, G. Andrijewski, U. Krajewska,
M. Rozalski, Eur. J. Inorg. Chem. (2007) 3728.
[20] N. Uramaru, H. Shigematsu, A. Toda, R. Eyanagi, S. Kitamura, S. Ohta, J. Med.
Chem. 53 (8727) (2010).
30 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31
[21] A. Pastrakuljic, R. Schwartz, C. Simon, L. Derewlany, B. Knie, G. Koren, Life Sci.
63 (1998) 2333.
[22] A. Grieco, A. Matera, P. Di-Rocco, S. Marcoccia, A. Giancaterini, B. Alfei, G.
Addolorato, F. Varlese, G. Gasbarrini, Hepatogastroenterology 45 (1998) 1731.
[23] (a) T. Watanabe, S. Yuki, M. Egawa, H. Nishi, J. Pharm. Exp. Ther. 268 (1994)
1597;
(b) H. Kawai, H. Nakai, M. Suga, S. Yuki, T. Watanabe, K.I. Saito, J. Pharm. Exp.
Ther. 281 (1997) 921.
[24] T.W. Wu, L.H. Zeng, J. Wu, K.P. Fung, Life Sci. 71 (2002) 2249.
[25] (a) M. Himly, B. Jahn-Schmid, K. Pittertschatscher, B. Bohle, K. Grubmayr, F.
Ferreira, H. Ebner, C. Ebner, J. Allergy Clin. Immunol. 111 (2003) 882;
(b) D. Costa, A.P. Marques, R.L. Reis, J.L.F.C. Lima, E. Fernandes, Free Radic. Biol.
Med. 40 (2006) 632.
[26] J.B. Field, E.C. Dolendo, A. Mireles, B.H. Ershoff, Cancer Res. 26 (1966) 1371.
[27] (a) F. Manetti, M. Magnani, D. Castagnolo, L. Passalacqua, M. Botta, F. Corelli,
M. Saddi, D. Deidda, A. De Logu, ChemMedChem 1 (2006) 973;
(b) D. Castagnolo, A. De Logu, M. Radi, B. Bechi, F. Manetti, M. Magnani, S.
Supino, R. Meleddu, L. Chisu, M. Botta, Bioorg. Med. Chem. 16 (2008) 8587;
(c) D. Castagnolo, F. Manetti, M. Radi, B. Bechi, M. Pagano, A. De Logu, R.
Meleddu, M. Saddi, M. Botta, Bioorg. Med. Chem. 17 (2009) 5716.
[28] F. Caruso, C. Pettinari, F. Marchetti, M. Rossi, C. Opazo, S. Kumar, S. Balwani,
B. Ghosh, Bioorg. Med. Chem. 17 (2009) 6166.
[29] A. Kimata, H. Nakagawa, R. Ohyama, T. Fukuuchi, S. Ohta, T. Suzuki, N. Miyata,
J. Med. Chem. 50 (2007) 5053.
[30] R.N.P. Nwankwoala, O.A. Georgewill, U.O. Georgewill, Res. J. Med. Sci. 4 (2009)
303.
[31] T. Filipský, P. Mladěnka, K. Macáková, R. Hrdina, L. Saso, F. Marchetti, C. Pet-
tinari, Biochimie 94 (2012) 125.
[32] L.-Y. Xu, N. Li, J.-M. Li, W. Dong, Z. Anorg. Allg. Chem. 639 (2013) 1800.
[33] Anurag Joshi, R.B. Shashi Verma, R.R. Gaur, Sharma, Bioinorg. Chem. Appl. 3
(2005) 201.
[34] B.A. Omotowa, M.A. Mesubi, Appl. Organomet. Chem. 11 (1997) 1–10.
[35] R. Pettinari, C. Pettinari, F. Marchetti, B.W. Skelton, A.H. White, L. Bonfili,
M. Cuccioloni, M. Mozzicafreddo, V. Cecarini, M. Angeletti, M. Nabissi, A.M.
Eleuteri, J. Med. Chem. 57 (2014) 4532.
[36] P.F. Liguori, A. Valentini, M. Palma, A. Bellusci, S. Bernardini, M. Ghedini, M.L.
Panno, C. Pettinari, F. Marchetti, A. Crispini, D. Pucci, Dalton Trans. 39 (2010)
4205.
[37] E.O. Platonova, E.V. Baranov, L.N. Bochkarev, A.Y. Kurskii, Russ. J. Coord. Chem.
38 (2012) 696.
[38] X. Yan, X. Wua, J. Xu, Y. Fan, C. Bi, X. Zhang, Z. Zhang, J. Mol. Struct. 1074 (2014)
609.
[39] O. Okpareke, E. Okafor, P. Ukoha, S. Okereke, Chem. Mater. Res. 6 (2014) 104.
[40] R.N. Jadeja, K.M. Vyas, V.K. Gupta, R.G. Joshi, C.R. Prabha, Polyhedron 31 (2012)
767.
[41] N.D. Ekekwe, A.J. Arinze, L.A. Nnanna, C.F. Ukpabi, A. Agwu, M.O.C. Ogwuegbu,
Am. J. Chem. 2 (2012) 52.
[42] (a) A. Glezies, A. Drozdov, S. Troyanov, Koord. Khim. 20 (1994) 922;
(b) A. Drozdov, S. Troyanov, J. Chem. Soc. Chem. Commun. (1993) 1619;
(c) D.C. Bradley, M. Hasan, M.B. Hursthouse, M. Motevalli, O.F.Z. Khan, R.C.
Pritchard, J.O. Williams, J. Chem. Soc. Chem. Commun. (1992) 575;
(d) R.E. Sievers, S.B. Turnipseed, L. Huang, A.F. Lagalante, Coord. Chem. Rev.
128 (1993) 285;
(e) C. Pettinari, F. Marchetti, R. Pettinari, V. Vertlib, A. Drozdov, I. Timokhin, S.
Troyanov, Y.-S. Min, D. Kim, Inorg. Chim. Acta 355 (2003) 157.
[43] C. Pettinari, F. Marchetti, A. Cingolani, D. Leonesi, S. Troyanov, A. Drozdov, J.
Chem. Soc. Dalton Trans. (1999) 1555.
[44] F. Marchetti, C. Pettinari, R. Pettinari, A. Cingolani, A. Drozdov, V. Vertlib, S.
Troyanov, Inorg. Chim. Acta 358 (2005) 1955.
[45] Y. Akama, T. Sawada, T. Ueda, J. Mol. Struct. 750 (2005) 44.
[46] Y. Akama, M. Kajitani, T. Sugiyama, A. Sugimori, Anal. Sci. 13 (1997) 155.
[47] T. Ueda, T. Sawada, Y. Akama, J. Mol. Struct. 750 (2005) 51.
[48] F. Caruso, M. Rossi, C. Opazo, C. Pettinari, Bioinorg. Chem. Appl. 3 (2005)
317.
[49] F. Caruso, M. Rossi, J. Tanski, R. Sartori, R. Sariego, S. Moya, S. Diez, E. Navarrete,
A. Cingolani, F. Marchetti, C. Pettinari, J. Med. Chem. 43 (2000) 3665.
[50] F. Caruso, L. Massa, A. Gindulyte, C. Pettinari, F. Marchetti, R. Pettinari, M.
Ricciutelli, J. Costamagna, J.C. Canales, J. Tanski, M. Rossi, Eur. J. Inorg. Chem.
(2003) 3221.
[51] F. Caruso, C. Pettinari, F. Marchetti, P. Natanti, C. Phillips, J. Tanski, M. Rossi,
Inorg. Chem. 46 (2007) 7553.
[52] P. Elo, A. Pärssinen, S. Rautiainen, M. Nieger, M. Leskelä, T. Repo, J. Organomet.
Chem. 695 (2010) 11.
[53] (a) I.N. Tretyakova, Y.V. Chernii, L.A. Tomachinskaya, S.V. Volkov, Theor. Exp.
Chem. 42 (2006) 175;
(b) L.A. Tomachynski, I.N. Tretyakova, V.Y. Chernii, S.V. Volkov, M. Kowalska,
J. Legendziewicz, Y.S. Gerasymchuk, S. Radzki, Inorg. Chim. Acta 361 (2008)
2569.
[54] F. Marchetti, C. Pettinari, C. Di Nicola, R. Pettinari, A. Crispini, M. Crucianelli,
A. Di Giuseppe, Appl. Catal. A 378 (2010) 211.
[55] S. Parihar, S. Pathan, R.N. Jadeja, A. Patel, V.K. Gupta, Inorg. Chem. 51 (2012)
1152.
[56] A. Di Giuseppe, C. Di Nicola, R. Pettinari, I. Ferino, D. Meloni, M. Passacantando,
M. Crucianelli, Catal. Sci. Technol. 3 (2013) 1972.
[57] S. Parihar, R.N. Jadeja, V.K. Gupta, RSC Adv. 4 (2014) 10295.
[58] C.K. Modi, Spectrochim. Acta A 71 (2009) 1741.
[59] S. Parihar, S.K. Gupta, R.N. Jadeja, P.K. Jha, Spectrochim. Acta A 128 (2014)
447.
[60] J. Li, J. Li, H. Zhang, J. Li, Cryst. Res. Technol. 44 (2009) 669.
[61] L. Hills, R. Moyano, F. Montilla, A. Pastor, A. Galindo, E. Álvarez, F. Marchetti,
C. Pettinari, Eur. J. Inorg. Chem. (2013) 3352.
[62] J.C. Arinze, N.E. Daniel, M.O.C. Ogwuegbu, JETEAS 3 (2012) 61.
[63] K.R. Surati, B.T. Thaker, G.R. Shah, Synth. React. Inorg. Met. NanoMet. Chem.
38 (2008) 272.
[64] L.R. Yang, C.Y. Shao, Z.L. Wang, J.T. Liu, F.L. Zhou, J. Chem. Crystallogr. 40 (2010)
58.
[65] V.F. Shulgin, N.S. Pevzner, O.V. Konnik, O.I. Konshina, G.G. Aleksandrov, I.L.
Eremenko, A.S. Bogomyakov, Russ. J. Inorg. Chem. 59 (2014) 58.
[66] F. Marchetti, C. Pettinari, R. Pettinari, A. Cerquetella, A. Cingolani, E.J. Chan,
K. Kozawa, B.W. Skelton, A.H. White, R. Wanke, M.L. Kuznetsov, L.M.D.R.S.
Martins, A.J.L. Pombeiro, Inorg. Chem. 46 (2007) 8245.
[67] S.L. Nongbri, B. Das, K.M. Rao, J. Organomet. Chem. 694 (2009) 3881.
[68] F. Caruso, E. Monti, J. Matthews, M. Rossi, M.B. Gariboldi, C. Pettinari, R. Pet-
tinari, F. Marchetti, Inorg. Chem. 53 (2014) 3668.
[69] R. Pettinari, F. Marchetti, C. Pettinari, A. Petrini, B.W. Skelton, A.H. White, L.
Bonfili, M. Cuccioloni, A.M. Eleuteri, J. Organomet. Chem. (2015), http://dx.
doi.org/10.1016/j.jorganchem.2015.04.049 (in press).
[70] O.C. Okpareke, J.N. Asegbeloyin, E.C. Okafor, O.T. Ujam, S.O.E. Okereke, Int. J.
Chem. Sci. 10 (2012) 1849.
[71] J.M. Shi, F.X. Zhang, C.J. Wu, L.D. Liu, Acta Crystallogr. E 61 (2005) m2320.
[72] J.-M. Li, J.-Z. Li, H.-Q. Zhang, L.-Y. Xu, Inorg. Chem. Commun. 13 (2010) 573.
[73] Y.J. Ding, C.X. Zhao, Asian J. Chem. 26 (2014) 3036.
[74] R. Xu, M. Liang, F. Yin, S. Li, Y. Huang, Y. Zhaoa, J. Liu, W. Ma, Inorg. Chem.
Commun. 40 (2014) 120.
[75] C. Pettinari, R. Pettinari, M. Fianchini, F. Marchetti, B.W. Skelton, A.H. White,
Inorg. Chem. 44 (2005) 7933.
[76] L. Shen, Z. Chen, Q. Zhao, F.-Y. Li, T. Yi, Y. Cao, C.-H. Huang, Inorg. Chem.
Commun. 9 (2006) 620.
[77] C. Yi, Q.-Y. Cao, C.-J. Yang, L.-Q. Huang, J.H. Wang, M. Xu, J. Liu, P. Qiu, X.-C.
Gao, Z.-F. Li, P. Wang, Inorg. Chim. Acta 359 (2006) 4355.
[78] Q. Zhao, C.-Y. Jiang, M. Shi, F.-Y. Li, T. Yi, Y. Cao, C.-H. Huang, Organometallics
25 (2006) 3631.
[79] H.-S. Lee, J.-H. Seo, M.K. Choi, Y.-K. Kim, Y. Ha, J. Phys. Chem. Solids 69 (2008)
1305.
[80] (a) H.-S. Lee, Y. Ha, Bull. Korean Chem. Soc. 32 (2011) 1007;
(b) H.S. Lee, S.Y. Ahn, H.S. Huh, Y. Ha, J. Organomet. Chem. 694 (2009) 3325.
[81] (a) H.-S. Lee, S.Y. Ahn, J.-H. Seo, Y.-K. Kim, Y. Ha, J. Korean Phys. Soc. 55 (2009)
1977;
(b) H.-S. Lee, S.Y. Ahn, Y. Ha, Mol. Cryst. Liq. Cryst. 514 (2009) 344;
(c) S.Y. Ahn, H.S. Lee, J.-H. Seo, Y.K. Kim, Y. Ha, Thin Solid Films 517 (2009)
4111;
(d) J.H. Seo, H.R. Park, Y.K. Kim, Y. Ha, J. Nanosci. Nanotechnol. 11 (2011)
7198.
[82] J. Li, J.-Z. Li, H.-Q. Zhang, Y. Zhang, J.-Q. Li, J. Coord. Chem. 62 (2009)
2465.
[83] H. Zhu, Z. Wei, L. Bu, X. Xu, J. Shi, Acta Crystallogr. E 66 (2011) m904.
[84] Y.E. Begantsova, L.N. Bochkarev, I.P. Malysheva, N.E. Stolyarova, Y.A. Kurskii,
M.A. Lopatin, E.V. Baranov, V.A. Ilichev, G.A. Abakumov, M.N. Bochkarev,
Synth. Met. 161 (2011) 1043.
[85] E.Y. Begantsova, L.N. Bochkarev, V.A. Ilichev, M.N. Bochkarev, Russ. Chem. Bull.
61 (2012) 1671.
[86] Y.E. Begantsova, L.N. Bochkarev, S.Y. Ketkov, E.V. Baranov, M.N. Bochkarev,
D.G. Yakhvarov, J. Organomet. Chem. 733 (2013) 1.
[87] S.A. De Pascali, D. Migoni, M. Monari, C. Pettinari, F. Marchetti, A. Muscella,
F.P. Fanizzi, Eur. J. Inorg. Chem. (2014) 1249.
[88] K.M. Vyas, R.N. Jadeja, D. Patel, R.V. Devkar, V.K. Gupta, Polyhedron 80 (2014)
20.
[89] L.N. Bochkarev, Y.P. Bariniva, A.I. Ilicheva, S.Y. Ketkov, E.V. Baranov, V.A.
Ilichev, D.G. Yakhvarov, Inorg. Chim. Acta 425 (2015) 189.
[90] A. Cingolani, F. Marchetti, C. Pettinari, R. Pettinari, B.W. Skelton, N. Somers,
A.H. White, Polyhedron 25 (2006) 124.
[91] (a) H.-Q. Zhang, J.-Z. Li, S. Gao, Y. Zhang, Acta Crystallogr. E 63 (2007) m165;
(b) X.-Z. Pang, J.-Z. Li, L.-S. Chen, H.-Q. Zhang, J. Coord. Chem. 66 (2013) 915.
[92] D. Pucci, A. Crispini, M. Ghedini, M. La Deda, P.F. Liguori, C. Pettinari, E.I. Szerb,
RSC Adv. 2 (2012) 9071.
[93] R.N. Jadeja, M. Chhatrola, V.K. Gupta, Polyhedron 63 (2013) 117.
[94] L.-Y. Xu, N. Li, J.-M. Li, W. Dong, Z. Anorg. Allg. Chem. (2013) 1800.
[95] J.-B. Xia, F.-Y. Li, H. Yang, X.-H. Li, C.-H. Huang, J. Mater. Sci. 42 (2007) 6412.
[96] H.-H. Zhang, X. Hu, W. Dou, W.-S. Liu, J. Fluor. Chem. 131 (2010) 883.
[97] L. Chen, J. Qiao, L. Duan, Y. Qiu, Synth. Met. 157 (2007) 713.
[98] R.K. Gupta, A. Jain, S. Saxena, Main Group Met. Chem. 32 (2011) 65.
[99] R.K. Gupta, A. Jain, S. Saxena, Main Group Met. Chem. 33 (2011) 9.
[100] A. Joshloa, S. Verma, R.B. Gaur, R.R. Sharma, Bioinorg. Chem. Appl. 3 (2005)
201.
[101] M.K. Srivastava, A. Jain, S. Saxena, Main Group Met. Chem. 37 (2014) 75.
[102] A. Jain, S. Saxena, A.K. Rai, P.N. Saxena, Bioinorg. Chem. Appl. 4 (2006) 1.
[103] (a) R.K. Gupta, A. Jain, S. Saxena, Main Group Met. Chem. 33 (2010) 167;
(b) K. Maheshwari, A. Jain, S. Saxena, Main Group Met. Chem. 37 (2014) 25.
[104] C. Pettinari, F. Marchetti, R. Pettinari, A. Cingolani, A. Drozdov, S. Troyanov, J.
Chem. Soc., Dalton Trans. (2002) 188.
[105] F. Caruso, C. Di Nicola, J.V. Hanna, F. Marchetti, C. Pettinari, R. Pettinari, M.
Rossi, G.J. Rees, B.W. Skelton, A.H. White, Inorg. Chim. Acta 367 (2011) 73.
 F. Marchetti et al. / Coordination Chemistry Reviews 303 (2015) 1–31
[106] F. Caruso, E.J. Chan, J.V. Hanna, F. Marchetti, C. Pettinari, C. Di Nicola, R. Petti-
nari, A. Pizzabiocca, G.J. Rees, D. Quigley, M. Rossi, B.W. Skelton, A.N. Sobolev,
A.H. White, Eur. J. Inorg. Chem. (2012) 1369.
[107] B. Zhao, X. Shang, L. Xu, W. Zhang, G. Xiang, Eur. J. Med. Chem. 76 (2014) 87.
[108] C. Pettinari, F. Marchetti, I. Timokhin, A. Marinelli, C. Di Nicola, B.W. Skelton,
A.H. White, Inorg. Chim. Acta 367 (2011) 98.
[109] C. Pettinari, F. Caruso, N. Zaffaroni, R. Villa, F. Marchetti, R. Pettinari, C. Phillips,
J. Tanski, M. Rossi, J. Inorg. Biochem. 100 (2006) 58.
[110] C. Pettinari, F. Marchetti, A. Cingolani, D. Leonesi, E. Mundorff, M. Rossi, F.
Caruso, J. Organomet. Chem. 557 (1998) 187.
[111] Y.-Z. Cheng, Y. Tang, F. Yan, Main Group Met. Chem. 37 (2014) 101.
[112] (a) J. Kido, Y. Okamoto, Chem. Rev. 102 (2002) 2357;
(b) J.-C.G. Bünzli, C. Piguet, Chem. Rev. 102 (2005) 1897;
(c) J.-C.G. Bünzli, C. Piguet, Chem. Soc. Rev. 34 (2005) 1048;
(d) L.-J. Xu, G.-T. Xu, Z.-N. Chen, Coord. Chem. Rev. 273–274 (2014) 47.
[113] A.Y. Belousov, A.A. Drozdov, Russ. Chem. Rev. 81 (2012) 1159.
[114] D. Zhang, M. Shi, Z. Liu, F. Li, T. Yi, C. Huang, Eur. J. Inorg. Chem. (2006)
2277.
[115] S.B. Meshkova, A.V. Kiriyak, Z.M. Topilova, V.P. Gorodnyuk, Opt. Spectrosc.
100 (2006) 836.
[116] C. Pettinari, F. Marchetti, R. Pettinari, A. Drozdov, S. Semenov, S.I. Troyanov,
V. Zolin, Inorg. Chem. Commun. 9 (2006) 634.
[117] M. Atanassova, V. Lachkova, N. Vassilev, S. Varbanov, I. Dukov, J. Incl. Phenom.
Macrocycl. Chem. 58 (2007) 173.
[118] J. Li, L. Zhang, L. Liu, G. Liu, D. Jia, G. Xu, Inorg. Chim. Acta 360 (2007) 1995.
[119] R. Van Deun, P. Nockemann, T.N. Parac-Vogt, K. Van Hecke, L. Van Meervelt,
C. Görller-Walrand, K. Binnemans, Polyhedron 26 (2007) 5441.
[120] Z.-F. Li, L. Zhou, J.-B. Yu, H.-J. Zhang, R.-P. Deng, Z.-P. Peng, Z.-Y. Guo, J. Phys.
Chem. C 111 (2007) 2295.
[121] Z. Li, J. Yu, J. Lumin. 143 (2013) 169.
[122] Z. Li, J. Yu, L. Zhou, H. Zhang, R. Deng, Inorg. Chem. Commun. 11 (2008)
1284.
[123] Z. Li, J. Yu, L. Zhou, H. Zhang, R. Deng, Z. Guo, Org. Electron. 9 (2008)
487.
[124] Z. Chen, F. Ding, F. Hao, Z. Bian, B. Ding, Y. Zhu, F. Chen, C. Huang, Org. Electron.
10 (2009) 939.
[125] X. Hao, S. Mei, M.Z. Xiao, Y.L. Fu, Q.B. Zu, K. Ibrahim, Q.L. Feng, H.H. Chun,
Chem. Mater. 15 (2003) 3728.
[126] X. Li, Z. Si, C. Pan, L. Zhou, Z. Li, X. Li, J. Tang, H. Zhang, Inorg. Chem. Commun.
12 (2009) 675.
[127] F. Marchetti, C. Pettinari, A. Pizzabiocca, A.A. Drozdov, S.I. Troyanov, C.O. Zhu-
ravlev, S.N. Semenov, Y.A. Belousov, I.G. Timokhin, Inorg. Chim. Acta 363
(2010) 4038.
[128] E.I. Szerb, A. Crispini, M. La Deda, D. Pucci, P.F. Liguori, C. Pettinari, Mol. Cryst.
Liq. Cryst. 549 (2011) 86.
[129] X.-L. Li, X. Niu, L.-F. He, X.-L. Feng, S.-M. Fang, L.-F. Ha, L.-M. Zhou, H.-P. Xiao,
Synth. Met. 161 (2011) 1063.
[130] A.V. Safronova, L.N. Bochkarev, I.P. Malysheva, E.V. Baranov, Inorg. Chim. Acta
392 (2012) 454.
[131] A.V. Safronova, L.N. Bochkarev, E.V. Baranov, Russ. J. Coord. Chem. 39 (2013)
537.
31
[132] N.M. Lazarev, A.Y. Bessonova, B.I. Petrov, G.A. Abakumov, L.N. Bochkarev, A.V.
Safronova, A.V. Arapova, A.V. Krasnov, G.V. Girichev, Russ. J. Coord. Chem. 40
(2014) 179.
[133] N.M. Lazarev, B.I. Petrov, L.N. Bochkarev, A.V. Safronova, G.A. Abaku-
mov, A.V. Arapova, A.Y. Bessonova, Russ. J. Phys. Chem. A 88 (2014)
1281.
[134] A. Listkowski, W. Osińska, J. Mohanrajc, M. Pietraszkiewicz, G. Dutkiewicz, T.
Borowiak, Synth. Met. 162 (2012) 1285.
[135] Z. Yang, R. Tang, Z. Zhang, J. Mol. Struct. 1030 (2012) 19.
[136] Z. Li, H. Zhang, J. Yu, Thin Solid Films 520 (2012) 3663.
[137] A.V. Rozhkov, L.N. Bochkarev, G.V. Basova, I.P. Malysheva, E.Y. Begantsova, E.O.
Platonova, E.V. Baranov, A.Y. Kurskii, V.A. Il’ichev, M.A. Lopatin, G.A. Abaku-
mov, M.N. Bochkarev, Russ. J. Gen. Chem. 82 (2012) 1895.
[138] L.N. Bochkarev, A.V. Rozhkov, V.A. Ilichev, G.A. Abakumov, M.N. Bochkarev,
Synth. Met. 190 (2014) 86.
[139] V.F. Shul’gin, S.V. Abkhairova, O.V. Konnik, S.B. Meshkova, Z.M. Topilova, M.A.
Kiskin, I.L. Eremenko, Russ. J. Inorg. Chem. 57 (2012) 420.
[140] V.F. Shul’gin, S.V. Abkhairova, O.V. Konnik, S.B. Meshkova, Z.M. Topilova, E.B.
Rusanov, G.G. Aleksandrov, I.L. Eremenko, Russ. J. Inorg. Chem. 58 (2013)
678.
[141] V.F. Shul’gin, O.V. Konnik, S.V. Abkhairova, A.N. Gusev, S.B. Meshkova, A.V.
Kiriyak, E.B. Rusanov, M. Hasegawa, W. Linert, Inorg. Chim. Acta 402 (2013)
33.
[142] O.V. Konnik, V.F. Shul’gin, Russ. J. Coord. Chem. 40 (2014) 28.
[143] A.Y. Belousov, A.A. Drozdov, P.P. Verteletskii, A.A. Prishchenko, L.I. Livantsova,
O.P. Novikova, Russ. J. Coord. Chem. 39 (2013) 278.
[144] A.Y. Belousov, V.V. Utochnikova, S.S. Kuznetsov, M.N. Andreev, V.D.
Dolzhenko, A.A. Drozdov, Russ. J. Coord. Chem. 40 (2014) 627.
[145] A.V. Safronova, L.N. Bochkarev, E.V. Baranov, Russ. J. Coord. Chem. 41 (2015)
118.
[146] C.X. Zhao, Y.J. Ding, T.T. Yuan, D.Y. Wanyan, Y.J. Guo, Z.Z. Hu, X. Li, Asian J.
Chem. 26 (2014) 8604.
[147] Z.-Q. Chen, F. Ding, Z.-Q. Bian, C.-H. Huang, Org. Electron. 11 (2010) 369.
[148] (a) L. Beverina, M. Crippa, M. Sassi, A. Monguzzi, F. Meinardi, R. Tubino, G.A.
Pagani, Chem. Commun. (2009) 5103;
(b) A. Sanguineti, A. Monguzzi, G. Vaccaro, F. Meinardi, E. Ronchi, M. Moret,
U. Cosentino, G. Moro, R. Simonutti, M. Mauri, R. Tubino, L. Beverina, Phys.
Chem. Chem. Phys. 14 (2012) 6452.
[149] P.N. Remya, S. Biju, M.L.P. Reddy, A.H. Cowley, M. Findlater, Inorg. Chem. 47
(2008) 7396.
[150] (a) J. Bao, C. Tang, R. Tang, J. Chin. Rare Earth Soc. 28 (2010) 531;
(b) J. Bao, C. Tang, R. Tang, J. Rare Earth 29 (2011) 15.
[151] S.N. Semenov, A.Y. Rogachev, S.V. Eliseeva, C. Pettinari, F. Marchetti, A.A. Droz-
dov, S.I. Troyanov, Chem. Commun. (2008) 1992.
[152] J. Xu, K.N. Raymond, Angew. Chem. Int. Ed. 45 (2006) 6480.
[153] L.-M. Zhu, S.-W. Wang, B.-L. Li, J.-R. Jin, Y. Zhang, J. Coord. Chem. 59 (2006)
1609.
[154] L.-M. Zhu, L.-Y. Wang, J.-R. Jin, B.-L. Li, Y. Zhang, J. Coord. Chem. 61 (2008) 917.
[155] L. Zhu, D. Yuan, B. Li, H. Li, J. Coord. Chem. 63 (2010) 3006.
[156] Y.M. Chumakov, P.A. Petrenko, F.G. Julea, V.I. Tsapkov, A.P. Gulea, J. Struct.
Chem. 55 (2014) 1116.