bk9781788016919 00001

Recent advances in chromium
coordination chemistry: luminescent

materials and photocatalysis
Paul A. Scattergood
DOI: 10.1039/9781788017077-00001
Downloaded from http://books.rsc.org/books/edited-volume/chapter-pdf/1604651/bk9781788016919-00001.pdf by University of Delhi user on 28 December 2023

With the design and development of sustainable photofunctional materials based upon
Earth-abundant elements being of growing interest, coordination complexes of Cr(III), with
their fascinating and long appreciated photophysical and photochemical properties, have
returned to prominence. This review charts the most recent developments towards new
photoluminescent complexes of Cr(III), discussing not only the synthetic strategies giving
access to increasingly more complicated molecular architectures but also highlighting
how an improved photophysical understanding of the electronic excited state underpins
the design of impressively efficient Cr(III)-based phosphors. This article concludes with a
survey of the first applications of Cr(III) complexes within visible light-driven catalysis.
1 Introduction and scope

Photoactive transition metal complexes have been of enormous interest
over the last half century, finding use in a diverse array of applications
ranging from light-emitting devices and new display technologies,1–3 to
optical sensing,4 biological imaging,5–7 artificial photosynthesis8,9 and
solar catalysis.10,11 Key to the success of these complexes is the facile
ability to tune their rich photophysical properties through not only
judicious choice of metal centre but also through careful design of the
surrounding ligand architecture, giving chemists access to a vast array of
photofunctional materials. However, whilst many of these examples show
great promise within light-driven systems and for the capture and con-
version of solar energy, they are frequently based upon rare and precious
transition metal cations such as Ru(II), Ir(III), Re(I) and Os(II). As society
strives to become ever more sustainable, it is clear that such complexes
are not economically viable. Consequently, attention has begun to shift
towards complexes of the first row transition metal elements which are
several orders of magnitude more abundant within the Earth’s crust.
Whilst such a shift may at first glance appear trivial, coordination
chemistry of the first row transition metals presents many fresh chal-
lenges, particularly to the synthetic chemist owing to underdeveloped
synthetic strategies, the regular occurrence of facile ligand exchange
reactions and frequently encountered poor photo-stability.
Whilst photoactive complexes based upon abundant metals such as
Cu(I)12–14 and Fe(II)15–18 have been the subject of notable attention, this
review focuses on the coordination chemistry of Cr(III). Although complexes
of Cr(III) have long been of interest as molecules with rich photophysical
properties and fascinating redox behaviour, research into these materials
Department of Chemistry, University of Huddersfield, Queensgate, Huddersfield

HD1 3DH, UK. E-mail: p.scattergood@hud.ac.uk
Organomet. Chem., 2021, 43, 1–34 | 1

c The Royal Society of Chemistry 2021
has recently undergone somewhat of a renaissance and returned to
prominence within the scientific literature. This review charts and sum-
marises these most recent advances, describing developments principally
over the last decade towards new photoluminescent chromium-based
complexes in addition to their applications within sustainable photo-
redox catalysis.

2 Notes
For simplicity, the micro-symmetry of the hexa-coordinate complexes
described within this review is approximated to octahedral and is thus
described using the Oh point-group classification. It is noted that a low-
ering of the symmetry can, in some instances, lead to further splitting of
excited states. Unless otherwise stated, quoted wavelengths of photo-
luminescence are those corresponding to emission from an excited state
of 2Eg(Oh) parentage.
3 Photophysics of Cr(III) complexes

In understanding the photophysical properties of Cr(III) coordination
complexes it is valuable to first consider both the nature of states and the
processes which may occur within the electronically excited state. As both
the photophysics and photochemistry of Cr(III) complexes are well
understood, the following descriptions serve only to summarise the key
concepts and fundamentals, with more detailed accounts having been
previously documented elsewhere.19–24
Unlike many well-known photo-active transition metal complexes, such
as the ubiquitous [Ru(bpy)3]21, which display photoluminescence as a
result of charge transfer transitions (e.g. metal-to-ligand (MLCT) or ligand-
to-metal (LMCT)), the photophysics of Cr(III) complexes is dominated by the
population of metal-centred (MC) (or ligand-field) excited states, which
when accompanied by a ‘spin–flip’ can give rise to particularly long-lived
luminescent excited states. In this review, all considered Cr(III) complexes
are hexa-coordinate with a d3 (t2g3, eg0) ground state electronic configur-
ation. For simplicity, the coordination geometry for many of these examples
can be approximated as being octahedral, thus the key electronic excited
states can be sufficiently described through a d3 Tanabe-Sugano diagram
derived for a complex with Oh symmetry (Fig. 1a). Thus the electronic
ground state for a typical Cr(III) complex is of quartet multiplicity (4A2g),
with photoexcitation resulting in a spin-allowed transition to populate a
Frank-Condon state corresponding to a vibrationally hot level of the 4T2g
excited state. As this electronic transition represents the population of
a metal–ligand anti-bonding orbital the excitation is accompanied by sig-
nificant structural distortion, hence the displacement of the 4T2g excited-
state surface relative to the ground state (Fig. 1c). From the simplified
Tanabe-Sugano diagram it may be seen that, beyond a critical ligand-field
strength, the identity of the lowest lying excited state switches from 4T2g to
2
Eg. Thus, in the presence of strong-field donors, the initially populated 4T2g
state may undergo inter-system crossing (ISC) to the thermally equilibrated
2 | Organomet. Chem., 2021, 43, 1–34

Organomet. Chem., 2021, 43, 1–34 | 3
Fig. 1 Simplified Tanabe-Sugano diagram for a d3 electronic configuration with Oh symmetry (a); Representations of the electronic configurations of the ground
and key excited states for a d3 Oh complex (b); Simplified schematic potential energy surface diagram showing the lowest energy quartet and doublet excited states
and the key processes of fluorescence (F), phosphorescence (P) and inter-system crossing (ISC).
2
Eg and 2T1g states. As these doublet states have essentially ground-state
geometry and bonding, their excited state surfaces are ‘nested’ with that of
the ground state, leading to relatively inefficient non-radiative deactivation
and the occurrence of long-lived and narrow ‘line-like’ photoluminescence.
It is pertinent to note that the energy of the 4T2g state can be readily
modulated by ligand-field strength, whilst the energy of the phosphor-
escent doublet states remain largely invariant. This observation is key to
rationalising the design of many efficient phosphorescent Cr(III)-centred

complexes, where maximising the ligand-field strength of the coordinated
ligands not only ensures that the 4T2g/2Eg crossing point is surpassed, but
also that the energy gap between the 2Eg and 4T2g states is sufficient to
avoid, or certainly minimise, detrimental back inter-system crossing (BISC).
Consequently, efforts to this end are prevalent within the various molecular
design strategies featured throughout this review towards achieving effi-
cient luminescent materials based on Cr(III).
4 Homoleptic polypyridyl complexes of Cr(III)

The photophysical properties of homoleptic polypyridyl complexes of Cr(III)
have long been of interest, where efforts have principally focused on com-
plexes of a,a 0 -diimines such as 2,2 0 -bipyridine (bpy), 1,10-phenanthroline
(phen) or substituted derivatives thereof.21–23,25 The parent complex of the
family [Cr(bpy)3]31 (1a) (Fig. 2) is luminescent in aqueous fluid solution
(summarised photophysical data for selected complexes are presented in
Table 1), displaying two emission bands at 694 nm and 728 nm which are
Fig. 2 Structures of homoleptic polypyridyl complexes of Cr(III).
4 | Organomet. Chem., 2021, 43, 1–34

typical for this class of complex.21,25 The latter, narrow band is the more
intense and assigned to luminescence from the 2Eg excited state, whereas
the former is only discernible as a high-energy shoulder, attributed to the
slightly higher lying 2T1g state. As the energy difference between these
two doublet states (690 cm1)25 is within the range of thermal energy,
conversion between these two states is rapid, resulting in the establishment
of an equilibrium distribution and identical excited state lifetimes of 63 ms
in deaerated 1M HCl(aq) solution.21 Exchange of 2,2 0 -bipyridine ligands

with 1,10-phenanthroline (2a) leads to a near identical photoluminescence
maximum, although the lifetime of emission increases 4-fold
(tem ¼ 270 ms), behaviour ascribed to the vibrationally more rigid phen
donors diminishing the rate of non-radiative decay.21 Upon chemical sub-
stitution of either bpy (1b–1c) or phen (2b–2c) the wavelength of emission is
largely unperturbed, consistent with luminescence deriving from the 2Eg
state, although notable enhancements in excited state lifetime are observed
(Table 1). Further, the homoleptic bis-terdentate complex [Cr(tpy)2]31
(tpy ¼ 2,2 0 :60 ,200 -terpyridine)(3) is only weakly emissive relative to 1a, with
a significantly shortened lifetime and red-shifted luminescence maximum
(lem ¼ 769 nm, tem ¼ 140 ns). The origin of the shift in emission and sta-
bilisation of 2Eg excited states is not clear, although has been tentatively
rationalised through a reduction in spin-pairing effects within individual
metal-based orbitals as a result of greater tg electron delocalisation over the
extended aromatic system of the tpy ligands.21,26,27
Alongside several photophysical investigations, many early reports
identified the strongly photooxidising behaviour and rich electrochemistry
of simple Cr(III) polypyridyls, although exact assignment of the nature of
redox events and the corresponding electronic structures remained unclear
and even contradictory. This was addressed in 2011 by Wieghardt and
Table 1 Summarised photophysical properties of homoleptic and polydentate polypyr-

idyl complexes of Cr(III).
Complex lem (2Eg)/nm tem/ms Ref. Complex lem (2Eg)/nm tem/ms Ref.
a a 21
1a 728 63 7 775b 899b 34
1b 731a 230a 21
8a 782b 770b 39
1c 742a 140a 21
8b 782b 1100b 39
1d 733a 7.7a 27
9 747c 1200c 46
2a 728a 270a 21
10 689d 0.004d 47
2b 734a 340a 21
11 671d 180d 47
2c 743a 370a 21
12 676d 0.0001d 47
3 770b 0.14b 26
13 667d 1.2d 47
6a 785b 0.30b 26
14 689d,e o0.01 48
6b 788b 0.40b 26
15 669c 235c 49
6c 785b 0.28b 26
16 Not observed 50
6d 796b 0.60b 26
17 740b 19b 50
26
6e Not observed 18 748f 4500f 51
a
Deaearted 1M HCl(aq).
b
Deaearted MeCN.
c
Deaearted H2O.
d
DMSO/HSO3CF3.
e
77 K.
f
Deaerated D2O/DClO4.
Organomet. Chem., 2021, 43, 1–34 | 5

co-workers who examined the electron transfer series [Cr(tBubpy)3]n1
(n ¼ 3, 2, 1, 0) (4a–4d) (tBubpy ¼ 4,4 0 -di-tert-butyl-2,2 0 -bipyridine) through
a comprehensive combined experimental and theoretical investigation.28
Their findings reveal that successive one-electron reduction occurs exclu-
sively at the ligands, forming bpy-centred p-radical anions (bpy ).
Here, the spins of the one-electron reduced bpy ligands are anti-
ferromagnetically coupled to those of the Cr(III)-centre (d3, S ¼ 3/2),
accounting for the S ¼ 3/2, 1, 12 and 0 ground states as determined by

magnetic susceptibility measurements for 4a–4d respectively. Importantly,
the central metal ion remains as Cr(III) throughout the series, revealing
that the dicationic species [Cr(tBubpy)3]21 cannot be described as having a
Cr(II) d4 low-spin configuration as has been typically and widely docu-
mented.29,30 The same co-workers also returned to examine the closely
related series [Cr(tpy)2]n1 (n ¼ 3,2,1,0) (5a–5d) again convincingly demon-
strating that sequential one-electron reductions are ligand-localised and
that the metal ion can be described as Cr(III) throughout.31 Interestingly,
further in-situ reduction permits the species [Cr(tpy)2] (5e) to be examined,
where the two coordinated dianionic tpy ligands exist in two different
spin configurations, either the singlet (tpy2)2 or triplet (tpy )2 states,
highlighting the rich and often under-appreciated redox chemistry of this
ubiquitous ligand and the hitherto unknown electronic structures of its
complexes with Cr(III).
One of the challenges hindering the development and use of Cr(III)
polypryidyl complexes within light-driven applications is the very weak
electronic absorption typically displayed by this class of complex within
the visible region. The series of homoleptic bis-terpyridine-based com-
plexes (6a–6e) (Fig. 2) reported by Lovaasen26 successfully exploit intra-
ligand charge transfer (ILCT) transitions to funnel visible light excitation
energy to the low-lying and emissive MC states. Functionalising
arylterpyridine ligands with electron-donating groups positions the
ligand-localised CT absorption within the visible region, lying below
those bands associated with p–p* ligand-centred excitations. 6a–6e
display enhanced absorption in the visible compared to [Cr(tpy)2]31 (3)
with 6d in particular exhibiting appreciable absorption at 450 nm
(e ¼ 11 900 M1 cm1) and 500 nm (5090 M1 cm1). Excitation into the
ILCT band of 6a–6d results in sharp 2Eg-derived emission bands between
785–796 nm (Table 1), slightly red-shifted relative to 3 (lem ¼ 770 nm) with
notably elongated lifetimes and in the case of 6d a four-fold increase in
intensity.26 Despite 6e exhibiting intense low-energy absorption features
(labs ¼ 532 nm e ¼ 56 500 M1 cm1, labs ¼ 691 nm e ¼ 13 600 M1 cm1)
direct excitation into these bands does not result in luminescence.
A recent report demonstrates that visible light irradiation of 6b populates
MC excited states which can singly (in the case of PPh3) or doubly
(for triethanolamine) oxidise sacrificial electron donors and thus function
as a multi-electron reservoir for photoinduced charge accumulation,32
whilst the group of Nair have taken advantage of the photoluminescence
of 6b and 6c in studying interactions with DNA, where quenching
of luminescence upon intercalation is indicative of photo-oxidation of
nucleobases and the cleavage of DNA.33
6 | Organomet. Chem., 2021, 43, 1–34

Although near-infrared (NIR) luminescence can be achieved with simple
homoleptic Cr(III) polypyridyl complexes, the quantum efficiencies are
typically very low. This is rationalised through the small energy difference
between the emitting 2Eg/2T1g states and the 4T2g level (Fig. 1a). Even for
popular strong-field donors such as bpy and tpy this energy gap remains
sufficiently small to facilitate efficient BISC, not only diminishing the effi-
ciency and lifetime of luminescence but also leading to photosubstitution
reactions owing to the lability of the 4T2g state. Indeed, the photoaquation of

several Cr(III) complexes, including [Cr(bpy)3]31 35 have been reported.19
Recently, Heinze and co-workers reported the synthesis of a Cr(III) complex
of the terdentate donor ddpd (N,N 0 -dimethyl-N,N 0 -dipyridine-2-yl-pyridine-
2,6-diamine) [Cr(ddpd)2]31 (7).34 Capable of forming 6-membered metal
chelates with bond angles close to 901 and behaving as a moderate s-donor
but poor p-acceptor, the ddpd motif was envisaged as being the ideal
strong-field ligand to enlarge the 4T2g/2Eg energy gap and thus realise effi-
cient, photo-stable NIR emitters.34,36,37 Indeed, the so-called ‘molecular
ruby’ 7 has a particularly large energy separation between 2Eg and 4T2g states
of 7100 cm1, with excitation into the LMCT absorption band at 435 nm
yielding phosphorescence (lem ¼ 775 nm) (Fig. 3) whose quantum effi-
ciency (Fem ¼ 12.1%) and lifetime (tem ¼ 899 ms) far surpass those seen with
more traditional Cr(III) polypyridyls. Further, 7 exhibits exceptional substi-
tutional stability, being inert to ligand loss in basic aqueous solution upon
prolonged irradiation over a period of 2.5 months. Through selective deu-
teration of methyl groups and by performing luminescence measurements
in deuterated solvent, Heinze and co-workers have further demonstrated
that non-radiative excited state decay pathways involving energy transfer to
high frequency ligand and solvent oscillators can be restricted, raising
the luminescence lifetime of 7 to 2.3 ms and the quantum yield of
Fig. 3 Normalised electronic absorption (left) and photoluminescence (right) spectra for
a solution of 7 in deaerated water. Adapted from ref. 34 with permission from John Wiley &
Sons, Copyright r 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Organomet. Chem., 2021, 43, 1–34 | 7

phosphorescence to a record level of 30.1%.38 Synthetic modification of the
ddpd framework to replace N–Me groups with N–H functionality affords the
terdentate ligand tpda and corresponding Cr(III) complex 8a.39 In acetoni-
trile solutions, 8a remains emissive (lem ¼ 782 nm), although with a lower
quantum yield (8.8%) and lifetime (770 ms) relative to 7 owing to multi-
phonon relaxation via the N–H oscillators. This is reduced upon deuter-
ation, with the N–D functionalised complex 8b exhibiting a 1.4 fold increase
in both the efficiency and lifetime of phosphorescence. Interestingly,

deprotonation of 8a reduces the intensity of luminescence, which is fully
quenched at pH 9.9 but recovers upon addition of acid, demonstrating
potential application as a luminescent pH sensor.39 Indeed, the unpre-
cedented photoluminescence of this ‘molecular ruby’ has lead to a plethora
of studies over the last 2–3 years aimed at exploring potential practical
applications. For example, dual emission from thermally equilibrated 2Eg
and 2T1g states has been exploited, with the temperature dependence of the
intensities of the two emission bands functioning as a ratiometric lumi-
nescent thermometer over the range 210–373 K,40 whilst external pressure
applied to either aqueous solutions or solid samples of 7 and 8a results in
red-shifted luminescence maxima from approximately 780 nm to 805 nm
(28 kBar).41 Biological nanosensors designed to simultaneously measure
temperature, oxygen and pH have incorporated 7 as the functional com-
ponent in the optical sensing of the former two stimuli.42 The role of 7 as a
water-soluble photosensitiser in photo dynamic therapy has been evalu-
ated, although the photocytotoxicity is found to be poor despite a moderate
quantum yield of 1O2 sensitisation of 61%.43 7 has been additionally trialled
by van Slageren and co-workers as a potential molecular quantum bit (MQB)
giving a record phase memory time at 7 K for a Cr(III) complex of 8.4 ms.44
Very recent studies have attempted to resolve chiral 7 into its corresponding
entantiomers.45 Despite the simplified pictorial depiction, 7 is not achiral,
with the ddpd ligands adopting a strongly twisted conformation about the
metal centre (see Fig. 4 for the molecular structure), giving rise to two dis-
tinct homo-chiral helicates (M, M and P, P) which exhibit considerable
configurational stability to racemisation. Thus, Seitz and co-workers have
successfully resolved 7 into its two enantiomers, with NIR circularly
polarised luminescence measurements indicating high luminescence dis-
symmetry factors (glum) of up to 0.093.45 Similarly, the group of Piguet have
synthesised 9 based upon the 2,6-di(quinolin-8-yl)pyridine ligand archi-
tecture.46 Displaying very long-lived luminescence in deaerated aqueous
solution (lem ¼ 747 nm, Fem ¼ 5.2%, t ¼ 1.2 ms), 9 adopts a non-planar
helical conformation which can be chirally resolved, with the resultant
enantiomers displaying exceptional luminescence dissymmetry
(glum ¼ 0.2), higher than that achieved with any d-block metal complex.
The 1990s saw a small number of reports concerning N-donor cage or
quasi-cage complexes of Cr(III), principally designed to investigate the
effects of trigonal distortion upon excited state lifetimes. Perkovic and
Endicott compared the closely related 10 and 1147 (Fig. 5), finding that
the phosphorescence lifetime of the former was 4.4104 shorter, despite
originating from a 2Eg state of near-identical energy. Likewise, complex
12 has a shorter luminescence lifetime by a factor of 104 than 13 which
8 | Organomet. Chem., 2021, 43, 1–34

Fig. 4 Molecular structure of complex 7.34 Co-crystallised solvent molecules and hydro-
gen atoms have been removed for clarity. Adapted from ref. 34 with permission from John
Wiley & Sons, Copyright r 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Fig. 5 Structures of N-donor cage and quasi-cage complexes of Cr(III).
has an analogous coordination environment around the metal centre.52

Similarly, Sargeson noted that the cage complex 14 displays a very short
(o10 ns) 2Eg state lifetime, which increases 2104-fold upon expansion to
the 6-membered chelate rings present in 15 (t ¼ 235 ms).48,49 Broadly, it
Organomet. Chem., 2021, 43, 1–34 | 9

may be concluded from these studies that trigonal twisting plays a major
role in excited state deactivation, with non-radiative relaxation being
promoted by those ligands whose geometrical constraints permit dis-
tortion from an octahedral towards trigonal prismatic geometry. The
theme of trigonal capped Cr(III) complexes was revisited in 2012 by the
group of Shores.50,53 16 shows improved absorption in the visible region
over its tris-bidentate iminopyridine analogue 17 although is non-
emissive, whereas 17 is weakly luminescent in deaerated acetonitrile

(lem ¼ 740 nm, Fem ¼ 6 102%, t ¼ 19 ms).50 Here the difference in
luminescence behaviour is not attributed to trigonal twisting induced by
ligand strain, owing to the flexibility of the ethyl bridges attached to the
capping N-atom, but rather the unexpected involvement of the
bridgehead N-atom in the frontier orbitals which induces the efficient
population of a low-energy non-emissive ligand-based quartet state.
A further 2019 study investigated the Cr(III) coordination chemistry of
the tripodal ligand 1,1,1-tris(pyrid-2-yl)ethane (tpe).51 Centrosymmetric
complex [Cr(tpe)2]31 18 is strongly emissive at room temperature
(lem ¼ 748 nm, F ¼ 3.2%) owing to particularly large ligand-field splitting
and a slow rate of non-radiative relaxation of the 2Eg state. The presence
of an inversion centre results in luminescence being both spin and
Laporte-forbidden, with the broadened profile of the emission band
indicating that vibronic coupling is required to facilitate this electronic
transition. Consequently, in D2O/DClO4 room temperature solution, 18
displays the longest luminescence lifetime (t ¼ 4500 ms) of any Cr(III)
emitter reported to date.51
5 Heteroleptic polypyridyl complexes of Cr(III)

The first heteroleptic polypyridyl complex of Cr(III) was reported in 2001,
with Wheeler, Kane-Maguire and co-workers disclosing an eloquent
synthetic route involving initial preparation of an intermediate complex
of the type cis-[Cr(diimine)2(CF3SO3)2]1 54 (Scheme 1). The weakly
coordinating triflate ligands are readily displaced through reaction with a
second diimine of choice when combined in a non-coordinating solvent.
The key advantage of this route is the reliance on the use of Cr(III) over
Cr(II) intermediates, with complexes of the latter being not only highly air
sensitive but also prone to facile ligand scrambling. Indeed, synthetic
attempts to form heteroleptic polypyridyl complexes via Cr(II) precursor
materials has been reported to lead to intractable mixtures of ligand
scrambled homo- and heteroleptic complexes.27 The authors of the initial
report were able to demonstrate the use of this route in the preparation
of 19–22, all of which are found to be emissive in deaerated aqueous
solution in the region of 730 nm (Table 2), characteristic of 2Eg-4A2g
phosphorescence and showing only modest variance in emission
energy and lifetime to the related homoleptic systems 1a & 2a. The group
of Housecroft have utilised the synthetic route shown in Scheme 1 to
prepare further heteroleptic complexes of Cr(III)55 whilst Ronco and
co-workers reported a range of bis-1,10-phenanthroline complexes of the
form [Cr(phen)2L]1 (23a–23f), where L is a substituted 2,2 0 -bipyridine or
10 | Organomet. Chem., 2021, 43, 1–34

Cl OTf (PF6)3
N N N
N N N Cl HSO3CF3 N OTf N N N N
CrCl3.6H2O Cr Cr Cr
Zn , EtOH N Cl r.t N OTf CH2Cl2 , Δ N N
Δ N N NH4PF6 N
19
54
Scheme 1 The synthetic route to heteroleptic diimine complexes of Cr(III) reported by Kane-Maguire et al., exemplified by the synthesis of 19.
Organomet. Chem., 2021, 43, 1–34 | 11

Table 2 Summarised photophysical data for heteroleptic polypyridyl complexes of Cr(III).
Complex lem (2Eg)/nm tem/ms Ref. Complex lem (2Eg)/nm tem/ms Ref.
a a 54
19 730 200 26b 730d Not reported 58
20 730a 112a 54
27 721a 7.6a 60
21 734a 280a 54
28a 733a 132a 61
22 737a 450a 54
28b 732a 154a 61
23a 730b 0.21b 56

28c 733a 198a 61
23b 729b 208b 56

28d 732a 170a 61

23c 732b 317b 56
29a 726b 214b 62
23d 730b 259b 56

29b 726b 259b 62
23e 730b 91b 56

29c 726b 177b 62
23f 728b 50b 56

29d 726b 17b 62
24a 732c 87c 27

29e 743b 23b 62
24b 742c 108c 27

30 Not reported 64
24c 734c 47c 27

31 Not reported 64
24d 733c 7.7c 27

32a Not reported 65
25a 728a 56a 57

32b Not reported 65
25b 728a 125a 57

33a 771b 1002 b 66
25c 728a 169a 57

33b 774b 980b 66
25d 735a 180a 57

34 779e 2.3, 40.3e 67
26a 730d Not reported 58
a
Deaerated H2O.
b
Deaerated MeCN.
c
Deaerated 1M HCl(aq).
d
Aerated H2O.
e
Powder at 5 K.
1,10-phenanthroline (Fig. 6).56 Whilst the wavelength of luminescence

displayed by 23a–23f is largely insensitive to the identity of the second
diimine ligand (L), the lifetime of phosphorescence varies dramatically,
ranging from 0.21 ms for 23a to 317 ms for 23c, largely dictated by
non-radiative deactivation mechanisms involving energy transfer to
ligand-localised high frequency oscillators. Importantly, the ability to
form heteroleptic complexes of Cr(III) with substituted diimines allows
for extensive scope in the tuning of redox potentials, vital for the devel-
opment of these complexes for photocatalytic applications.
24a–24d were investigated by Shores et al. in 2010.27 Accessed via the
synthetic protocol described above, the methyl-ester groups serve to
protect carboxylic acid functionality, a well known anchoring group for
attachment to metal oxide surfaces, essential for molecules which have
the potential to inject positive holes into semiconductor substrates
upon irradiation. Aside from electronic transitions within the UV
region, complexes 24a–24d show appreciable absorption extending into
the visible region, with 24b in particular exhibiting bands at 450 nm
(e ¼ 1960 M1 cm1) and 480 nm (e ¼ 1490 M1 cm1). Excitation of 24a,
24c and 24d at 320 nm results in weak phosphorescence (Fo0.6%)
observed at approximately 733 nm, although interestingly red-shifted
to lem ¼ 742 nm for the bathophenanthroline-containing complex 24b.
This latter observation suggests a subtle lowering in energy of the 2Eg
state, tentatively rationalised by the authors as being due to the effects of
intraligand electronic delocalisation over the larger p-system reducing the
12 | Organomet. Chem., 2021, 43, 1–34

Fig. 6 Structures of heteroleptic polypyridyl complexes of Cr(III).
energetic perturbation of individual metal orbitals upon spin-pairing

within the doublet configuration. 24a–24d display rich electrochemistry,
with the carboxyl ester functionality shifting the first reduction potentials
to remarkably anodic potentials. With excited state reduction potentials
in the region of þ1.2 V vs Fc/Fc1, these systems are identified as par-
ticularly potent photooxidants.27
Also in 2010, Kane-Maguire and co-workers reported the synthesis of
heteroleptic Cr(III) complexes 25a–25d containing the well-known DNA in-
tercalator fragment dipyridophenazine (dppz) (Fig. 7).57 All complexes were
reported to display typical Cr(III) phosphorescence in the region
728–735 nm, with lifetimes of 33–54 ms in aerated solution. Photo-
luminescence is heavily quenched upon the addition of calf thymus B-DNA,
attributed to photo-induced electron transfer and the photooxidation
of guanine bases. Indeed, excited state reduction potentials of 25a–25d
Organomet. Chem., 2021, 43, 1–34 | 13

(B 1.50 V vs SHE) are not only tuneable as a function of the identity of the
ancillary diimine ligands but reveal the Cr(III) complexes to be thermo-
dynamically competent for guanine oxidation. Kelly, Quinn and co-workers
examining 25b and then closely related 26a–26b, found that luminescence
was almost completely quenched upon addition of DNA, with chemical
substitution of the dppz moiety effecting the equilibrium binding constant
but leaving the energy of the 2Eg emitting state unperturbed.58 Later, a
combined ultrafast transient absorption (TA) and time-resolved infra-red

(TRIR) study on 25b bound to defined sequence DNA found that the excited
state of the intercalated complex was very rapidly quenched, with the
absence of detectable electron transfer products suggesting that photo-
oxidation of guanine is immediately followed by extremely rapid back
electron transfer (o3 ps).59 These studies have been further supplemented
by the investigation of the interaction of 27 with both mono- and poly-
nucleotides.60 Based on the first report of tris-heteroleptic Cr(III) complexes
(28a–28d),61 the synthesis of which proceeds via the successive precursors
[Cr(diimine)Cl3(dmf)] (dmf ¼ N,N-dimethylformamide) and cis-[Cr(diimi-
ne)(diimine 0 )(CF3SO3)2]1, methylimidazole-containing 27 is luminescent at
721 nm in the absence of DNA,60 with photoaquation of the monodentate
ligands offering scope for future investigations into the formation of
covalent photoadducts with DNA.
Aside from intercalation studies with biological materials, heteroleptic
polypyridyl complexes of Cr(III) have more recently been examined as
tunable optical sensitisers. A 2018 report from Doistau et al.62 describes the
synthesis and photophysical properties of 29a–29e, highlighting that the
lifetime of 2Eg-derived luminescence can be tuned through judicious
incorporation of low-energy vibrational modes and additional rotational
degrees of freedom within the ligand structure, the latter being evident
for 29e where the shorter lifetime is attributed to enhanced crossing from
2
Eg to 4A2g states as a result of the anharmonic misalignment of excited state
potential energy surfaces. Further, synthetic routes to asymmetric hetero-
leptic complexes have also allowed photoluminescent Cr(III) complexes to
feature within extended polymetallic architectures, with a 2020 report
describing the potential for Cr(III)-centred fragments to function as very
long-lived NIR sensitisers within light-converting polymetallic devices.63
In addition to those heteroleptic complexes of Cr(III) featuring
didentate ligands, the first examples containing two different terdentate
ligands were reported by Housecroft and Constable in 2014.64 Relying
upon an analogous synthetic methodology to that described in Scheme 1,
30–31 (Fig. 8) are accessed through a [Cr(tpy)(OTf)3] precursor, with the
resultant complexes displaying intense electronic absorption bands
within the UV-region. Absorption bands are shifted into the visible region
for complexes 32a–32b,65 with intra-ligand charge transfer bands
appearing at 507 and 523 nm respectively, somewhat stabilised relative to
transitions occurring in the free-ligand as a result of ligation to Cr(III).
Surprisingly, whilst 30–31 and [Cr(tpy)2]31 (3) are thermally stable in
aqueous solution at pH 6.36 and below, these complexes are labile in the
presence of base. The authors demonstrate that the likely photoproducts
are Cr(ligand)(solvent)3 in nature, with at least one of the terdentate
14 | Organomet. Chem., 2021, 43, 1–34

Fig. 7 Further structures of heteroleptic polypyridyl complexes of Cr(III).
Organomet. Chem., 2021, 43, 1–34 | 15

3+ 3+ 3+
N N N N
N N N N R
Cr Cr N Cr N N
N N N N R
N N N N
30 31 R = Ph 32a
4-OMe-Ph 32b

3+
6+
N N
N N N N N
R N Cr N N Cr N N Cr N
N
N N N N N
N
34
R= H 33a
CO2Et 33b
Fig. 8 Structures of terpyridine-derived heteroleptic complexes of Cr(III).
ligands being retained, going further in noting that ligand dissociation

also occurs in methanolic solutions of 30–31 in the presence of added
[Bu4N][F], leading to the formation of [Cr(ligand)(F)3] species.64
Piguet and co-workers have applied the aforementioned synthetic
strategy towards heteroleptic bis(terdentate) complexes of Cr(III) along-
side the design features of the ‘molecular ruby’ 7, combining the ddpd
ligand with tpy-derivatives in complexes 33a–33b (Fig. 8).66 Noting the
acid sensitivity of some desirable ligands, this synthetic work eloquently
proceeds via the route illustrated in Scheme 2, where the weaker Cr-Br
bonds are more readily cleaved by AgOTf than those in CrCl3 under
microwave irradiation, giving access to useful [Cr(L)(OTf)3] precursors
whilst avoiding the use of strongly acidic reaction media. Here, the
inclusion of a ddpd ligand partially compensates for the unfavourable
distortion imparted by the 5-membered chelate rings of tpy, giving
complexes which are photoluminescent (lemE771 nm, F ¼ 0.06–0.14%)
with impressive lifetimes of tE1 ms. As supramolecular chemistry is
perhaps more developed for terpyridine-derivatives, these results are of
significance for the incorporation of light-emitting Cr(III) fragments
within expanded photo-functional molecular architectures. Indeed, het-
eroleptic terdentate ‘back-to-back’ Cr(III) dyads such as 34 have been
synthesised as simple proof of concept models for the investigation of
inter-metallic communication within multi-metallic systems.67
6 Acetylide complexes of Cr(III)

The first structurally characterised acetylide complex of chromium was
reported by Berben and Long in 2002.68 Synthesised through the addition
of Me3SiCCLi to [(Me3tacn)Cr(CF3SO3)3] (Me3tacn ¼ N,N 0 ,N00 -trimethyl-
1,4,7-triazacyclononane) with later deprotection of the silyl group, this
16 | Organomet. Chem., 2021, 43, 1–34

Organomet. Chem., 2021, 43, 1–34 | 17

Scheme 2 An alternative step-wise synthetic route to heteroleptic complexes of Cr(III) containing acid-sensitive polypyridyl ligands.66
preparative route to 35 paved the way towards a multitude of acetylide
complexes of Cr(III). With bis trans-alkynyl complexes being of growing
interest towards the development of molecular wires, several structures,
such as 36 and 37, emerged as promising linear connector synthons for
the construction of extended delocalised rigid-rod systems.69–72 Further,
Shores et al. have utilised Cr-acetylide building blocks in the construction
of dinitrogen-bridged bi-metallic dimers such as 38.73 Whilst these
studies reveal a range of fascinating redox and magnetic properties, the

photophysical attributes of these systems are rarely reported. On the
other hand, trans bis-acetylide complexes of Cr(III) featuring tetraaza
macrocycles are of significant photophysical interest.74,75
trans-Cr(cyclam)bis(acetylide) (cyclam ¼ 1,4,8,11-tetraazacyclotetrade-
cane) complexes may be prepared through the combination of [Cr(cyclam)-
(OTf)2]1 with lithiated acetylides,76 the synthetic methodology utilised by
Wagenknecht and co-workers in the formation of 39a–c (Fig. 9).77 These
early examples display ligand-field electronic absorption bands between
330–450 nm and are phosphorescent in aerated acetonitrile solutions
(lem ¼ 748 nm) with lifetimes of 5–6 ms, notably increasing to around 30 ms
in deaerated H2O. Whilst it may be reasonably expected that such com-
plexes would display typical 2Eg-derived emission, the low-energy broad
and featureless emission profiles indicate that these systems are in fact 2T1g
emitters, an observation that warrants further explanation.
Fig. 9 Structures of acetylide-containing complexes of Cr(III).
18 | Organomet. Chem., 2021, 43, 1–34

Fig. 10 An energy level diagram showing the splitting of Oh states with increasing
quadrate field. Adapted from ref. 81 with permission from American Chemical Society,
Copyright 1985.
As has been described earlier within this review, Cr(III) complexes whose
micro-symmetry can be approximated as octahedral (Oh) possess two
emissive doublet states, 2Eg and 2T1g. However, as quadrate splitting
increases and symmetry lowers towards D4h, it can be seen that the 2Eg (D4h)
state of 2T1g origin (described hereafter as 2T1g (Oh)) drops to a lower energy
than those states derived from a 2Eg (Oh) level (described hereafter as
2
Eg(Oh)) (Fig. 10).20,78–80 Thus, the identity of the lowest lying luminescent
state is heavily dependent upon the magnitude of quadrate splitting, which
in turn is influenced by the difference in p-bonding characteristics between
axial and equatorial ligands. This is especially applicable to the bis-alkynyl
tetraaza Cr(III) systems described here, where the N-atoms of the macrocycle
act as s-donors and the apical alkynyls tend, although not always, to behave
as both s- and p-donors. Usefully, emission from 2Eg(Oh)-derived states
tends to be structured, falling within the region 650–710 nm, whereas
2
T1g(Oh)-derived luminescence is identified by red-shifted broad and fea-
tureless emission profiles.78
Studies of Cr(III)(cyclam)-containing complexes were expanded by the
same workers in 2011, revisiting 39a–d whilst also reporting on the new
series of trans bis-acetylides 40a–d (Fig. 9).82 Interestingly, in addition to
cis/trans isomers being separable on the basis of solubility, the employed
one-pot synthetic strategy requires the addition of a 2-fold excess of nBuLi
in order to suppress a competing hydroamination reaction between the
arylacetylene and cyclam N–H functionality. The authors also note the
requirement to employ lithium diisopropylamide as a base in the syn-
thesis of 40c, although this complex could not be obtained with satis-
factory purity to permit further photophysical analysis. 40a–b display
typical ligand-field absorptions between 320–550 nm, with modest molar
extinction coefficients (eE170–700 M1 dm3) suggesting a degree of
‘intensity-stealing’83 from proximal charge transfer bands. Additionally,
Organomet. Chem., 2021, 43, 1–34 | 19

the extended aromaticity in 40a–b leads to the onset of electronic
absorption being red-shifted to approximately 550 nm when compared to
39a. Further, comparison of cis-39a vs trans-39a reveals excitations of very
similar energy, although being twice as intense in the former due to the
lack of a centre of symmetry. 40a–b are both luminescent in the region of
750 nm, displaying broad, featureless 2T1g (Oh) emission bands (Fig. 11a),
with lifetimes similarly being unperturbed by the identity of the
arylacetylide moiety, measured as 3 ms in aerated acetonitrile solution.

A near-identical emission profile observed for 40e reveals that even
perfluorinated arylacetylides retain sufficient p-donor character that the
2
T1g(Oh)-derived excited state remains the lowest lying.78 Conversely,
40d containing comparatively poor p-donor cyclohexyl-alkynyl ligands
displays notably different luminescence behaviour; with a blue-shifted
emission maximum (lem ¼ 727 nm) (Fig. 11b) and fine-structuring being
indicative of additional contributions from the 2Eg (Oh) excited state,
perhaps further evidenced by the observation of two different lifetimes at
77 K.82 Deuteration of the cyclam N–H groups in 39a elongates lumi-
nescence lifetime approximately 4-fold, whereas deuteration upon the
aryl ring has little effect, demonstrating the role of cyclam-based N–H
oscillators in mediating non-radiative deactivation of the excited state
within these systems.82 The trifluoropropynyl moiety has been investi-
gated as an electronic surrogate for closely related cyano ligands
(vide infra).84 40f displays near-identical ligand-field absorption bands to
trans-[Cr(cyclam)(CN)2]1 (48a) at 420 and 340 nm, although the emission
for 40f is weak, with clear fine structuring centred around 725 nm sug-
gesting an emitting state of 2Eg (Oh) character. This is in stark contrast to
39a–40b described above, indicating that these electron-deficient alkynyl
ligands no longer act as p-donors but rather moderate p-acceptors. Of
further note is an additional paper from the group of Wagenknecht85
which finds that changing the reaction solvent from THF to Et2O raises
the proportion of cis isomer formed from 14 to 48%. Thus, cis-40f is also
found to be a 2Eg(Oh)-emitter, although with loss of centrosymmetry
giving rise to a dominant 0–0 transition at lem ¼ 738 nm.
The synthetic versatility afforded by alkynyl functionality has been
exploited by several workers to further expand the Cr trans bis-alkynyl
core, introducing redox active units such as ferrocene for example95 or
through the assembly of extended non-linear p-conjugated frameworks
such as geminal-diethynylethenes (gem-DEE).91 Comparing 40g and 41a,
the greater electron density introduced by the extended p-system is
manifest in enhanced electronic absorption between 340–500 nm, whilst
the improved p-donor capabilities red-shift the luminescence maximum
of 41a (lem ¼ 750 nm) over that of 40g (lem ¼ 736 nm). Contrastingly, both
40h and 41b are not emissive in solution nor at 77 K in a solvent glass,
behaviour ascribed to the occurrence of energy-transfer quenching of the
Cr(III)-centred doublet excited state by the ferrocene moieties.91
The scope of Cr(III) bis-alkynyl complexes has recently been expanded
by the group of Ren, employing the DMC tetraaza ligand (DMC ¼ 5,12-
dimethyl-1,4,8,11-tetraazacyclotetradecane) in complexes 42a–c and 43
(Fig. 12).86 Interestingly, the preparation of 42a–b heavily favours the
20 | Organomet. Chem., 2021, 43, 1–34

Organomet. Chem., 2021, 43, 1–34 | 21
Fig. 11 Photoluminescence spectra recorded for complexes 40a (a) and 40d (b) in room temperature aqueous solution and at 77 K in a H2O/DMSO glass. Adapted
from ref. 82 with permission from American Chemical Society, Copyright 2011.
trans isomer regardless of whether cis- or trans-[Cr(DMC)Cl2]1 starting
materials are employed, whereas the use of butadiynyl ligands (42c and 43) is
more stereospecific, requiring employment of starting materials with the
desired stereochemistry. In other instances, the conformation of the mac-
rocycle itself ultimately dictates the geometry around the metal centre.
5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (HMC) exhibits
rac and meso diasteroisomers, with addition of lithiated alkynes to cis/rac-
[Cr(HMC)Cl2]1 giving cis products (44a–b) whereas the use of trans/meso-

precursors leads to exclusive formation of trans species 45a–b.87 Electronic
absorbance spectra for these Cr(III) cyclam derivatives reveal transitions
10–30 times more intense than their dichloride precursors, owing to strong
mixing with proximal alkynyl-based charge transfer transitions. Remarkably,
the d-d absorption envelope is highly structured, with vibronic progressions
for 42c, 43, 44b and 45b falling within the range of C C stretching modes,
potentially indicating coupling of these oscillators to the Cr centre.86,87 The
absorbance profile for 43 is quite similar to that of its counterpart 42c,
although marginally shifted to lower energy and being more intense, the
latter feature consistent with the lack of an inversion centre. Similarly to 40h
described above, 42b is essentially non-emissive, whereas 42a, 42c, 43 and
HMC complexes 44a–45b display fairly broad, weak (Fo0.15%) emission
bands between 746 and 777 nm (Table 3), allowing them to be categorised as
2
T1g (Oh)-emitters. 43 displays a shorter luminescence lifetime (t ¼ 160 ms) at
77 K than its structural isomer 42c (t ¼ 358 ms), consistent with 45b and 44b
where the trans-isomer (t ¼ 455 ms) exhibits an enhanced lifetime over the cis
analogue (t ¼ 129 ms). These observations are tentatively ascribed to
increased geometric strain within cis systems and consequent operation of
non-radiative decay pathways.86,87
Further Cr(III)-centred complexes of HMC have been prepared
which feature 1-ethynylnaphthalene ligands.88 Both 46 and 47 display
Fig. 12 Structures of DMC- and HMC-containing bis-acetylide complexes of Cr(III).
22 | Organomet. Chem., 2021, 43, 1–34

Table 3 Summarised photophysical data for bis-alkynyl and bis-cyano complexes of
Cr(III).
Complex lem/nma tem/ms Ref. Complex lem/nma tem/ms Ref.

b b 77 b b 86
39a 748 225 42c 755 113
39b 749b 259b 77
43 777b 68b 86
39c 748b 203b 77

44a 764b 212e 87
82
39d Not reported 44b 771b 129e 87
40a 749b 250 b 82

45a 746b 469e 87

40b 750b 238b 82
45b 746b 455e 87
82
40c Not reported 46 747b 218b 88
40d 727b 331b 82

47 777b 97e 88
40e 747c Not reported 78

48a 720f 335f 89
40f 725d 460d 84

48b 720f 1500f 89
40g 736b 351b 91

49 735g 0.24g 90
91
40h Not observed 50 724h 23g 92
41a 750b 185 b 91

51 705h 24g 93
91
41b Not observed 52 712i 190i 94
42a 750b 95b 86

53 721h 147g 93
86
42b Not observed
a
Maximum of lowest energy emission band.
b
Deaerated MeCN.
c
MeCN.
d
Deaerated H2O.
e
4 : 1 EtOH/MeOH glass at 77 K.
f
5103 M HNO3(aq).
g
0.01M HCl(aq).
h
DMSO/H2O at 77 K.
i
DMSO/H2O.
red-shifted d-d electronic absorption bands relative to 44a and 45a due to
the increased aromaticity of the aryl substituent. Luminescence from 46
and 47 is predominantly 2T1g(Oh) in nature (lem ¼ 747 and 777 nm
respectively), although an additional small high-energy shoulder
(lem ¼ 727 nm) observed for 46 at 77 K indicates partial dual emission
from a 2Eg(Oh) state, similar behaviour to that seen for 42a. Despite
employing a well-known fluorophore, naphthalene-based emission is not
detected for these complexes, indicating efficient quenching by the metal
centre.
7 Macrocyclic bis-cyano complexes of Cr(III)

The preparation of trans-[Cr(cyclam)(CN)2]1 (48a) was reported in 1983
and unlike several contemporary complexes (e.g. trans-[Cr(NH3)4(CN)2]1
and trans-[Cr(en)2(CN)2]1) was found to be completely inert to photo-
substitution.89 48a displays intense phosphorescence at 720 nm with a
lifetime of 335 ms, elongated 5-fold upon selective deuteration of the
cyclam (48b) (see Table 3 for summarised photophysical data). Further,
deprotonation/protonation of cyclam N–H groups allows the phosphor-
escence to be quenched and then fully restored. 48a and 48b featured in a
later 2002 study,79 where flash photolysis was used to probe energy-
transfer dynamics between the longer-lived deuterated species and its
proteo analogue, essentially representing self-exchange energy transfer.
Organomet. Chem., 2021, 43, 1–34 | 23

+ + +
R R H R R
N N N N N N
N Cr N N Cr N N Cr N
N N N N N N
R R H R R
R = H 48a 49 50
D 48b
+ + +

H H H H H H
N N N N N N
N Cr N N Cr N N Cr N
N N N N N N
H H H H H H
51 52 53
Fig. 13 Structures of macrocyclic bis-cyano complexes of Cr(III).
Bis-cyano Cr(III) complexes featuring cyclam derivatives have con-

tinued to be of further interest, with complexes 49 and 50 containing
constrained macrocycles 1,4-C2-cyclam and 1,11-C3-cyclam respectively
being reported (Fig. 13).90,92,96 Synthesis of these systems proceeds via
the usual [Cr(cyclam 0 )Cl2]1 precursors, which along with the resultant
cyano complexes are produced with exclusively trans geometry.
Whilst X-ray crystal structures show the coordination sphere bond
lengths to be consistent, the strain imparted by the additional macro-
cycle linkages leads to distortion of bond angles away from idealised
values of 901 and 1801 as found in 48a, with the CrN4 plane being
additionally distorted in 49.92 Perhaps surprisingly, whilst 48a is pho-
toinert, both 49 and 50 display moderate rates of photoaquation, with
loss of axial CN ligands. Electronic absorption spectra of 48a–50
exhibit ligand-field transitions of very similar energy, although mar-
ginally shifted to lower energy for 50 and then 49 owing to the weaker
ligand-field caused by the aforementioned structural distortions hin-
dering efficient donor-metal orbital overlap. Remarkably, the molar
absorptivity of these transitions clearly increases in the order
48ao50o49, concomitant with the progressive deviation from octa-
hedral symmetry, perfectly illustrating the consequences of relaxation
of the Laporte rule. 49 and 50 are luminescent at 735 and 724 nm
respectively, although they are much weaker emitters than 48a with cor-
respondingly shorter lifetimes (t ¼ 0.24 ms for 49 and 23 ms for 50). Unlike
48a, these emission profiles are dominated by intense 0–0 transitions,
further representing the lowering in symmetry. Curiously, 49 and 50 show
no enhancement of luminescence lifetime upon N–H deuteration when in
aqueous solution, although deuterated 50 exhibits a 4-fold enhancement in
phosphorescence lifetime when in a frozen glass.92
51–53 have also been investigated as luminescent bis-cyano com-
plexes of Cr(III), featuring very subtle structural modifications of the
macrocyclic motif (Fig. 13).93 The progressively increasing ligand-field
strength imposed by the expanded macrocycles [16]aneN4, [15]aneN494
24 | Organomet. Chem., 2021, 43, 1–34

and then isocyclam is evident in electronic absorption spectra where the
energetic ordering of the d-d transitions follows the trend 51o52o53.
These systems are categorised as 2Eg(Oh) emitters, with largely similar
peak positions centred around 720 nm (Table 3). The lower degree of
centrosymmetry around the coordination sphere in 53 imparted by
isocyclam is represented by an emission spectrum at 77 K dominated by
the 0–0 transition, whereas the highly symmetrical macrocyle within 51
gives rise to clear vibronic structuring. In room temperature aqueous

solution, 53 displays a shorter lifetime (t ¼ 147 ms) than the parent
complex 48a (t ¼ 335 ms), although this is elongated compared to 51
(t ¼ 24 ms). Once more, with non-radiative decay of emissive 2Eg(Oh)
excited states involving tunnelling to the 4A2g(Oh) ground state, deu-
teration of the high-frequency N–H oscillators in 53 extends the lifetime
in aqueous solution almost 3-fold.93
8 Photoluminescent Cr(0) complexes

Although this review is primarily concerned with photoactive complexes
of Cr(III), it is worth briefly noting a particularly impressive example of a
recently reported photoluminescent Cr(0) complex. Despite 77K emission
from Cr(0) species being noted over 40 years ago,97 it was only in 2017
that the group of Wenger made use of bulky chelating diisocyanide lig-
ands in obtaining 54 (Fig. 14).98–100 This zero-valent complex is orange/
red in colour, exhibiting 1MLCT electronic absorption bands between
400–600 nm and displaying luminescence in room temperature THF
solution at 630 nm with a quantum yield of 105 and lifetime of 2.2 ns.98
Significantly, the lifetime of the 3MLCT excited state is at least an order of
magnitude longer than currently achievable with isoelectronic complexes
of the Earth-abundant metal Fe(II), sufficiently long to allow energy
transfer to acceptors and subsequent photon upconversion. Further, 54 is
a particularly potent photoreductant, with an excited state oxidation
potential of 2.43 V vs Fc/Fc1.98
Fig. 14 A luminescent tris(diisocyanide) Cr(0) complex reported by Wenger et al. Adapted

from ref. 98, https://pubs.acs.org/doi/10.1021/acsami.7b00046, with permission from
American Chemical Society, Copyright 2017.
Organomet. Chem., 2021, 43, 1–34 | 25

9 Cr(III) complexes in photoredox catalysis
Over the last decade photoredox catalysis has emerged as an increasingly
popular synthetic tool for the mediation of a variety of useful organic
transformations. Whilst commonly employed photocatalysts rely upon
the use of precious metals such as iridium and ruthenium, attention has
recently shifted towards complexes of Earth-abundant elements.101–104
Although Cr(III) complexes have long been recognised for their photo-

oxidising capabilities, their first use as photoredox catalysts in organic
synthesis was reported in 2015 by Ferreira, Shores and Stevenson.105 Simple
tris Cr(III) polypyridyls such as 1d, 2a & 24a (Ered* ¼ þ 1.45 to þ 1.84 V vs SCE)
were found to catalyse the [4 þ 2] dimerisation of 1,3-cyclohexadiene, gen-
erally giving better yields than the related but less powerful photooxidant
[Ru(bpz)3]21 (bpz ¼ 2,2 0 -bipyrazine) (Ered* ¼ þ 1.45 V vs SCE) under the same
conditions. The bathophenanthroline-containing complex 2c, with its
slightly lower oxidising power (þ1.40 v vs SCE) was identified as being ideal
for facilitating cross-cycloadditions between dienes and electron-rich
dieneophiles, selectivity oxidising the latter. Indeed, 2c successfully cata-
lyses the cycloaddition of trans-anethole with isoprene with an excellent
yield of 88% under near-UV irradiation in nitromethane. Interestingly the
authors of this initial report noted the requirement for the presence of
oxygen in achieving catalytically activity. This was later rationalised through
a detailed mechanistic study, where the dual role of oxygen as both an
electron and energy transfer shuttle was revealed.106 As illustrated in the
proposed mechanism (Scheme 3), 3O2, or rather subsequently formed 1O2
and superoxide, play a critical role in either regenerating the Cr(III) catalyst
or reducing the radical cationic cycloaddition product. This is a mech-
anistically distinct picture from that found in similar reactions catalysed
by [Ru(bpz)3]21 where a radical chain propagation occurs, a consequence
here of the exceptionally long-lived 2Eg excited state of the Cr(III) catalyst
(2c, t ¼ 13 ms under reaction conditions) permitting the build-up of an
appreciable concentration of 1O2 and thus initialising the oxygen-mediated
photocatalytic cycle. Further finer details of this complicated mechanism
Scheme 3 Proposed mechanism102,103,106 for an oxygen-mediated light-driven [4 þ 2]

cycloaddition reaction catalysed by 2c. Adapted from ref. 103 with permission from the
Royal Society of Chemistry.
26 | Organomet. Chem., 2021, 43, 1–34

Scheme 4 Possible pathways for the 2c-catalysed light-driven [4 þ 2] cycloaddition
reaction with electron deficient dienophiles. Adapted from ref. 108 with permission
from the Royal Society of Chemistry.
have been resolved computationally by Dang et al. who suggest the role of a
quintet intermediate complex [CrL3-O2]21 in the final electron transfer step
to the radical cationic cycloadduct.107
Under visible-light irradiation, 2c also catalyses the [4 þ 2] cycloaddition
between dienes and electron-deficient dieneophiles (Scheme 4).108 This is
somewhat surprising given that enone 55 has an oxidation potential at
least 0.6 V higher than the excited state reduction potential of 2c, yet the
cycloaddition product is observed to form with a yield of 85%. Mech-
anistically, this clearly requires a different explanation to that described
above. With direct oxidation of the enone, and indeed the diene being
thermodynamically unfavourable, additional pathways were suggested
(Scheme 4). Route A relies upon the photoexcitation of the dieneophile and
subsequent [2 þ 2] cycloaddition with the diene to form a vinylcyclobutane
intermediate (56). In the presence of 2c under irradiation, 56 may undergo
single-electron oxidation rearrangement to give the product (57). Route B
involves in situ dimerisation of starting enone 55 to give a cyclobutane
dimer 58. Photooxidation may then induce cycloreversion and trapping of
the resultant radical cation (59) by the diene giving product 57, although
control experiments suggest this route plays a minor role in the formation
of 57. Finally, route C recognises that the photoexcited enone 60 is more
easily oxidised than when in its ground state, with the resultant radical
cation once more reacting with an equivalent of diene to give the
cycloaddition product. Molecular oxygen again appears to be beneficial to
photocatalytic performance, although not essential in this instance. The
substrate scope of this reaction has been expanded to include a wide range
of both substituted dienes and electron deficient chalcone-derivatives,
all undergoing cycloaddition with good to excellent yields. Notably, these
reactions proceed with reverse regioselectivity to that seen in conventional
Diels–Alder cyloadditions.108
Organomet. Chem., 2021, 43, 1–34 | 27

Cr complexes 1d, 2a, 2c & 24a have been found to catalyse the
cyclopropantion of diazo compounds with electron rich alkenes under
visible light irradiation (Scheme 5a), with 2c giving the highest yield of
cyclopropane 63 (60%) under comparable conditions.109 Expanding the
substrate scope, 2c is particularly suited to catalysing the [2 þ 1]
cycloaddition between 62 and a range of substituted stilbenes, in add-
ition to successful examples involving the reaction of 61 with a-alkyl
diazo esters. In these latter instances, it is notable that diazo dimer-

isation does not occur, nor are b-hydride elimination products
detected.109 Further, 2c has been additionally exploited in the photo-
catalysed [3 þ 2] cycloaddition of alkenes and vinyl diazo substrates to
form functionalised cyclopentenes (Scheme 5b).110 The reaction mech-
anism appears to involve initial oxidation of trans-anethole by the photo-
excited Cr catalyst, generating an electron deficient radical cation which
then undergoes direct nucleophilic attack by the vinyl diazo reagent.
High diasteroselectivities are reported for these transformations, with the
cycloadducts being readily diversified though tolerance of a wide variety
of substituted coupling partners under the employed reaction conditions.
Arai and Ohkuma have utilised [Cr(bpy)3]21 (1a) to catalyse the aza-
Diels–Alder cycloaddition reaction of N-arylimines with various alkenes
under blue-light irradiation (Scheme 5c).111 N-arylimines bearing both
electron-withdrawing and –donating groups upon the aryl moiety react
smoothly with vinyl-pyrrolidinones over 3–10 hours to give the 1,2,3,4-
tetrahydroquinoline derivatives in moderate to excellent yields with
catalyst loadings as low as 0.1 mol%.
Moving away from more traditional Cr(III) polypyridyls, a 2017 study
from the group of Heinze has yet further exemplified the wide utility of the
‘molecular ruby’ complex 7 by demonstrating its use as a photocatalyst for
(a)
Ph hν Ph
N2 CH3NO2 or DCE
CO2Et
Ph EtO2C 2c Ph
61 62 63
(b) MeO
OMe hν
CO2Et
CO2Et CH3NO2 / CH2Cl2
N2 2c
66
64 65
(c) O
N
R' hν , MeCN
O R'
N R'' N
1a N R''
H
67
68 69
Scheme 5 Examples of Cr-catalysed cycloaddition reactions: (a) [2 þ 1] cyclopropanation;

(b) [3 þ 2] cyclopentene formation; (c) tetrahydroquinoline formation from vinyl-
pyrrolidinones.
28 | Organomet. Chem., 2021, 43, 1–34

Scheme 6 Cr-catalysed formation of an a-aminonitrile from a tertiary amine.112
C–H bond functionalisation of tertiary amines (Scheme 6).112 In this

instance, a mechanism involving photo-induced electron transfer from the
excited catalyst is ruled out, but rather the reaction proceeds via Dexter
energy transfer from the long-lived 2Eg state to 3O2, efficiently generating
singlet oxygen (F 1O2 ¼ 61%). A subsequent charge transfer complex
between 1O2 and the amine substrate may then lead to hydride transfer,
giving hydroperoxide and an iminium ion, the latter being quenched by a
cyanide source. Impressively, 7 can catalyse the formation of 71 in 89%
yield after only 20 minutes irradiation time, being not only re-usable but
also giving appreciable conversions (23%, 20 mins) when used at loadings
as low as 0.01 mol%.112
10 Concluding remarks
As chemists look to develop sustainable photofunctional materials based
upon Earth-abundant elements, it is unsurprising that considerable
recent attention has been paid to new coordination complexes of Cr(III).
Whilst long appreciated for their rich electrochemical and magnetic
properties, recent advances have seized upon the remarkable photo-
physical properties offered by complexes of Cr(III), exploiting the ‘spin–
flip’ which occurs in the electronic excited state to achieve particularly
long-lived luminescence in the near-infrared spectral region from ligand-
field excited states.
With many traditional examples of luminescent Cr(III) complexes being
restricted to those homoleptic systems of polypyridyl ligands, this review
has highlighted efforts, mostly over the last decade, towards the use of
novel ligand architectures whose molecular design is informed by an
improved understanding of the nature of the electronic excited state, in
addition to the discovery of new synthetic routes towards previously
unknown heteroleptic complexes. Further valuable efforts have been
spent in exploiting ligand-centred transitions in extending the electronic
absorption profile into the visible region, whilst also gaining a vital
understanding of the solution stability and photoreactivity of these sys-
tems. Thus, particularly impressive complexes typified by the so-called
‘molecular ruby’ have emerged whose photophysical attributes now
closely rival those displayed by complexes of popular precious metals
such as Ru(II) and Ir(III), lending themselves to use in a plethora of light-
driven applications.
The potential utility of photo-active complexes of Cr(III) is no better
exemplified than by the reports, from only over the last 5 years, of the use
of these materials as efficient photo-redox catalysts. Relying upon the
most plentiful of energy sources, sunlight, these inexpensive catalysts
Organomet. Chem., 2021, 43, 1–34 | 29

open avenues towards new and transformative environmentally friendly
organic synthesis.
Whilst the near future clearly offers researchers many exciting oppor-
tunities for the development of sustainable photofunctional materials
based upon Earth-abundant elements, there remains significant chal-
lenges to overcome. These are principally concerned with achieving a
greater degree of control over the synthesis of these new complexes,
improving their long-term thermal- and photo-stability and most import-

antly, extending their electronic absorption profiles and photon-harvesting
abilities to cover a greater portion of the solar emission spectrum.
However, whilst there clearly remains room for furthering our under-
standing of the chemical reactivity and photophysical properties of
complexes of Cr(III), the new and exciting photo-active examples detailed
in this review highlight that Cr(III) is indeed emerging as a credible
alternative to the precious metals that we have relied upon over the last
half century within photofunctional materials.
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Recent advances in chromium

coordination chemistry: luminescent

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1 Introduction and scope

Department of Chemistry, University of Huddersfield, Queensgate, Huddersfield

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3 Photophysics of Cr(III) complexes

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4 Homoleptic polypyridyl complexes of Cr(III)

Fig. 2 Structures of homoleptic polypyridyl complexes of Cr(III).

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Table 1 Summarised photophysical properties of homoleptic and polydentate polypyr-

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8 | Organomet. Chem., 2021, 43, 1–34

Fig. 5 Structures of N-donor cage and quasi-cage complexes of Cr(III).

has an analogous coordination environment around the metal centre.52

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5 Heteroleptic polypyridyl complexes of Cr(III)

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23a 730b 0.21b 56

23b 729b 208b 56

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23d 730b 259b 56

23e 730b 91b 56

23f 728b 50b 56

24a 732c 87c 27

24b 742c 108c 27

24c 734c 47c 27

24d 733c 7.7c 27

25a 728a 56a 57

25b 728a 125a 57

25c 728a 169a 57

25d 735a 180a 57

26a 730d Not reported 58

1,10-phenanthroline (Fig. 6).56 Whilst the wavelength of luminescence

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Fig. 6 Structures of heteroleptic polypyridyl complexes of Cr(III).

energetic perturbation of individual metal orbitals upon spin-pairing

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Fig. 8 Structures of terpyridine-derived heteroleptic complexes of Cr(III).

ligands being retained, going further in noting that ligand dissociation

6 Acetylide complexes of Cr(III)

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Fig. 9 Structures of acetylide-containing complexes of Cr(III).

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