Photophysics of transition metal complexes

Francesco Nastasi, Maria Letizia Di Pietro, Emanuela Trovato and

Fausto Puntoriero*

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DOI: 10.1039/9781849737722-00156

This chapter deals with studies on the photophysical properties of selected metal
complexes and their polynuclear supramolecular assemblies reported in literature in
the period January 2011 to December 2012. The transition metal species considered
here belong to families of complexes featuring largely studied optical properties. The
complexes are from the following metal centres: d6 Ru(II), Os(II), Re(I), Ir(III) and
Rh(III), d8 Pt(II) and Pd(II), d10 Cu(I) and Au(I), d3 Cr(III); nally some example is
given of lanthanide (Ln) complexes or supramolecular arrays.

Introduction

The study of the photophysical and photochemical properties of coordination and organometallic compounds is at the center of a large and
growing interest. Several reasons are at the basis of such an interest,
including the use of coordination and organometallic compounds as
photo-active components in processes aimed to perform articial photosynthesis (e.g., photochemical water splitting and CO2 photoreduction),
the design of new dye-sensitized solar cells, the development of new
luminescent sensors for environment and biological systems, the development of new systems for illumination, the preparation of nanostructures
capable of exhibiting new optical properties and luminescence imaging to
be used in diagnostic and medicine. Whereas research in these above
mentioned elds is relatively new (or has been strongly revitalized by
recent results) and has literally exploded in the last decade, the photochemical and photophysical properties of metal compounds continue to be
investigated also for fundamental reasons, such as for detailed studies
aimed to increase the knowledge on photoinduced energy and electron
transfer in supramolecular systems.
The result of the impressive work focused on the photophysics of
metal compounds in the last years makes impossible to write a really
comprehensive report on this eld.1 The area is a broad one and in order
to adopt criteria for introducing the choice from the available material,
we have made eorts to provide an extended layout of quoted papers;
this should allow the interested reader to be aware of the main part of
the literature available. For instance, in recent years the use of neutral
luminescent species in the fabrication of OLEDs, particularly of Ir(III)
complexes, has become an important eld of activity for the photophysical characterization of the luminophores; consideration of this aspect
therefore has provided a criterium for grouping contributions. Among the

Dipartimento di Scienze Chimiche - Universita` degli Studi di Messina, Viale F. Stagno

dAlcontres, 31, I-98166 Messina Italy and SolarChem - Centro di Ricerca Interuniversitario
per la Conversione Chimica dellEnergia Solare. E-mail: fpuntoriero@unime.it

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transition metal complexes, also the various families of lanthanide

derivatives constitute both a distinct and enormeous and expanding area,
and for these reasons a summary on this topic is reported at the end of this
review.
In 2011 an highlight paper has been focused on various luminescent
complexes with dierent transition metal centres of d6, d8 and d10 electronic
congurations. Through the systematic study on the variation of ligands,
structural and bonding modes of dierent metal centres, the structureproperty relationships of the various classes of luminescent transition metal
complexes have been reported.2
It is essentially clear that an approach like function by design could
be employed to explore and exploit the potential applications of such
luminescent transition metal complexes. Future development of luminescent
transition metal complexes with improved and optimized functions in
the widely diverse elds of immunoassay, chemosensing, OLEDs, OPVs
and DSSCs, multimodal imaging, diagnostics, therapy, photocatalysis, and photosensitizers for clean and renewable energy is clearly
envisaged.313
Several review articles on the use of transition metal complexes as
chemosensors have been published too.14 In the context of luminescent
sensing, transition metal complexes have unique advantages that make them
suitable for chemosensing or biosensing applications: (i) high luminescence
quantum yield, (ii) long excited state lifetime, (iii) large Stokes shift,
(iv) sensitivity of their photophysical properties to changes in the local
environment. In light of these advantages ruthenium(II), platinum(II),
iridium(III), osmium(II), gold(I) and rhenium(I) compounds have been
widely studied for luminescent sensing applications.15
2

Ruthenium and osmium

The long-lasting trend for studying complexes based on Ru(II) and Os(II)
centres is continuously going up. In the time interval considered, a lot of
new papers have appeared which report the synthesys and properties of such
species. Relevant lines of activity employed Ru(II) complexes as active
probes towards various substrates, or as active centres for light/energy
interconversion devices.1620
Ru(II) complexes decorated with a bithienyl amide pendant have been
shown to exhibit a very long-lived charge separated state (in the range of 3 to
7 ms ligand centered-CT) storing at least 2 eV of energy.21 Excited state
tuning of a series of supramolecular building blocks based on 2,2 0 :4,400 :4 0 ,4 000 quaterpyridine (qtpy) as ligand and Ru(II) as metal centre has been
investigated. The excited states were shown to be qtpy centered except
where the ancillary ligands are dppz.22 Reviews on supramolecular dyads
in which perylene-3,4:9,10-bis(dicarboximide) (DPI) is combined with a
bpyRuCl2(CNtBu)2 fragment have been reported and the new studied species
show an exoergonic (DGCS of about 1 eV) PET from Ru to DPI. The TA
spectroscopy reveals that the charge recombination process happens in 63 ps.23
A [Ru(bpy)2(dppz)]2 complex with a dppz ligand decorated by benzimidazolylcoumarin group exhibits a non-emissive 3IL state but is able to
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24

sensitize triplettriplet annihilation up-conversion with DPA.

The
presence of two acetyl carbazole moyeties appended to a phen ligand
allows an homoleptic Ru(II) complex to show NIR two-photon
absorption.25
The species [Ru(bpy)2(dppz)]2 is non luminescent in aqueous solution or
in the presence of amyloid-beta peptide monomers but exhibits long-lived
luminescence upon peptide aggregation, this property allows to use it in
time-resolved imaging microscopy.26
It is quite well known that the pure D and L enantiomers of
[Ru(phen)2(dppz)]2 and [Ru(bpy)2(dppz)]2exhibit biexponential excitedstate emission decays when bound to mixed-sequence DNA. By a combined
analysis of calorimetric and photophysical data for binding of the D and L
enantiomers, the two emission lifetimes have been assigned to two distinct
intercalation geometries.
One strategy to prolong excited-state lifetimes for bis(tridentate) ruthenium(II) complexes is to bestow a more idealized octahedral ligand environment. Within this eld a series of heteroleptic bis(tridentate)
ruthenium(II) complexes, each bearing a substituted 2,2 0 :6 0 ,200 -terpyridine
(terpy) ligand, has been reported to be characterized by room temperature
microsecond excited-state lifetimes. These results are the consequence of the
strongly s-donating and weakly p-accepting tridentate carbene ligand, 2 0 ,6 0 bis(1-mesityl-3-methyl-1,2,3-triazol-4-yl-5-idene)pyridine (CLNLC), adjacent to the terpy maintaining a large separation between the ligand eld and
metal-to-ligand charge transfer (MLCT) states while also preserving a large
3
MLCT energy.27
By exploiting the complexes-as-metals/complexes-as-ligands synthetic
strategy, six new dinuclear achiral complexes of RuII, containing the tripodal ligand tris(1-pyrazolyl)methane, a chelating ligand such as 2,2 0 bipyridine, 1,10-phenanthroline or 2,2 0 -biquinoline, and either pyrazine or
4,4 0 -bipyridine as bridging ligands, have been prepared and characterized.
Spectroelectrochemical experiments have conrmed that in mixed-valence
(II/III) species pz is a good electron coupling mediator between the metal
centers. On the contrary, 4,4 0 -bpy does not help the intermetallic
communication.28
In 2011 a number of reports have appeared dealing with the
photophysical properties of complexes based on 1,2,3-triazole ligands.
The mixed valence complex [(tpy)-Ru(ttapyr)Ru(tpy)]3 (ttapyr=1,3,6,8tetrakis(1-butyl-1,2,3-triazol-4-yl)pyrene) exhibits intervalence charge
transfer transitions.29 Dyads based on [Ru(bpy)3]2 and naphthalenebisdiimide-acceptor fragment connected by a 1,2,3-triazole linker show
ecient electron transfer through the triazole moiety.30
Proton-coupled electron transfer (PCET) from tyrosine (TyrOH) to a
covalently linked [Ru(bpy)3]2 photosensitizer in aqueous media has been
reinvestigated by laser ash-quench kinetics as a model system for PCET in
radical enzymes and in photochemical energy conversion. The results
showed the mechanistic sensitivity and complexity of PCET reactions with
water as proton acceptor and provide experimental model systems for
several dierent PCET mechanisms.31

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Dye-sensitised solar cells (DSSCs) remain an active area for the application
of ruthenium complexes. Several reports have appeared for the development
of ecient cyclometallated thiocyanate-free complexes as new ecient dyes
for DSSC applications. Complexes of the type A32 and B33 for example, show
eciencies of ca. 8%. Remote substituent eects on DSSC performance have
been investigated in complexes of the form [Ru(dcb)(4,40-(p-C6H4X)2-2,20bpy)(NCS)2]. An eciency of 8.3% was obtained in devices based on a dye
where X= OMe.34 [Ru(dcb)(4-{pyrid-2-yl}-1,2,3-triazole)-(NCS)2] based
complexes result in DSSC devices with high eciency (7.8%), despite reduced
optical absorption compared to established dyes such as N3.35 In 2012 a new
ambidentate dicarboxylic acid ligand, dfm, that provides a continuous conjugation pathway from 2,2 0 -bipyridine (bpy) to a metal oxide surface was
synthesized and coordinated to [Ru(bpy)2]- fragment for sensitization of
TiO2. An ecient rinj = 0.70  0.05 interfacial electron transfer to TiO2 was
observed even though the [Ru(bpy)2(dfm)]2 MLCT excited state lifetime was
o10 ns, providing a new alternative to the commonly utilized 4,4 0 -(CO2H)22,2 0 -bipyridine (dcb) ligand for the coordination of transition metal compounds to metal oxide surfaces.36
B

A new family complexes containing Ru(II) as the central metal atom and 5diethylamino-1,10-phenanthroline (5-Et2Nphen) as an environmentally sensitive
ligand has been synthesized and their potential as pH reporters examinated.37
The photophysical properties of osmium compounds are to a large extent
very similar to those of ruthenium ones. Indeed, most of the luminescent Os

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compounds are Os(II) polypyridine complexes, analogous to the ruthenium

ones.
The photophysics of Os(II) imine complexes and the light induced energy
and electron transfer reactions involving them have been extensively reviewed.
A series of [Os(N6N)2(P6P)] complexes (N6N=5-(1-isoquinolyl)-1,2,4triazolate) with relevance to OLEDs containing chelating diphosphine
ligands P6P has been investigated by DFT and TDDFT methods. Results
indicate that they are better electron than hole transporters.38
Osmium(II) complexes containing N-heterocyclic carbene (NHC)-based
pincer ligand 1,3-bis(1-methylimidazolin-2-ylidene)phenyl anion (C16C6C1)
or 1,3-bis(3-methylbenzimidazolin-2-ylidene)phenyl anion (C26C6C2) and
aromatic diimine (2,2 0 -bipyridine (bpy), 1,10-phenanthroline (phen), or 4,4 0 diphenyl-2,2 0 -bipyridine (Ph2bpy)) in the form of [Os(C6C6C)(N6N)(CO)]
have been prepared and investigated from a theoretical and experimental
point of view. The results indicate that these complexes are emissive with long
lifetimes, and the emissive excited-states are shown to be derived from
HOMO-LUMO transitions. Moreover the authors demonstrated that these
ligands can aect the photophysical properties via the formation of the hybrid
[Os C6C6C] frontier orbitals.39
A series of newly synthesized Os(II) complexes bearing isoquinolinetriazolate/pyrazolate ligands showed a remarkable ratiometric intensity
changes in phosphorescence versus uorescence that are excitation wavelength dependent.40
The rst example of an [Os(tpy)2]-like species able to intercalate into
DNA has been reported in 2012. This compound is completely quenched in
aqueous solution and becomes luminescent in the near-IR spectral region in
the presence of a small amount of biopolymer. Thus, this osmium species
behaves as a real OFF-ON DNA light switch.41
3

Rhenium

The photochemistry of rhenium compounds occupies a prominent position

in the photochemistry of transition-metal compounds. As pointed out in
recent books and reviews,42 the current photochemistry of rhenium compounds is extremely rich, spanning eight oxidation states, from formal Re(0)
to formal Re(VII).
In 2012 the rst Re(I)-dipyrrinato complexes have been reported. Complexes with the general formulae fac-[ReL(CO)3Cl], fac-[ReL(CO)3PR3],
and [ReL(CO)2(PR3)(PR 0 3)], where L is one of a series of meso-aryl
dipyrrinato ligands and R or R 0 are phenyl or butyl, have been prepared
and studied. The results showed that the new species are luminescent from
an excited state centred on dipyrrinato ligand.43
The introduction of a uorous moiety on the structure of polypyridine
Re(I) complexes has oered unique properties for rendering them
novel biological probes. The new reported species are three luminescent
rhenium(I) polypyridine uorous complexes [Re(Me2bpy)(CO)3(L)]
(Me2bpy=4,40 -dimethyl-2,2 0 -bipyridine; L=3-amino-5-(N-((3-peruorooctyl)propyl)aminocarbonyl)pyridine, 3-ethylthioureidyl-5-(N-((3-peruorooctyl)propyl)aminocarbonyl)pyridine, that oer interesting luminescence behavior to the
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labeled molecules, which would allow new assay design and the possibility
of studying the cellular uptake of the labeled molecules by confocal
microscopy.44
The species of general formula [Re(N6N)(CO)3L]n(N6N=bpy, phen,
4,7-dimethyl-phen; L=Cl, n=0; L=imidazole, n=1) have been studied by
ultrafast spectroscopy. Between them [Re(bpy)(CO)3(L)] complexes (L is a
monodentate 1,2,3-ligand) have been reported to exhibit long luminescent
lifetimes (in the ms time-scale) in air equilibrated solutions at RT.45 The
ultrafast spectroscopy experiments demonstrated that the latter complex
undergoes to rapid ISC (in about 150 fs) populating two long-lived triplet
states.46
In 2011 the cluster [Re6S8Cl5(4-ppy)]3 (4-ppy=4-phenylpyridine) was
prepared and the photophysical studies show that this species emits in the
red in CH3CN. In detail the transient absorption spectroscopy revealed that
the emissive state is a CT that involves Re6-core as donor and ppy as
acceptor.47 The emission properties of a new family of Re(I) diimine
carbonyl complexes containing isocyano ligands was demonstrated to be ne
tuned.48 [Re(N6N)(CO)3(5-aryltetrazolate)] complexes have been prepared
and the photophysical studies show excited state lifetimes that range from 100
to 900 ns with quantum yields from 1% to 10%.49 New cyclometalated
complexes with general formula [Re(CO)3(N6C)X](N6C=3-butyl-1-(2pyridyl)benzimidazolin-2-ylidene, X=Cl, Br) exhibit emission from a
partially mixed 3MLCT/3LLCT state.50
Re(I) tricarbonyl complexes with pyrazolylpyridyl based chelate ligands
are luminescent with quantum yields up to 0.05 and exhibit electrochemiluminescence properties.51
4

Iridium

No doubt, iridium is the metal whose study of the photophysical properties

of the coordination and organometallic compounds has experienced the
largest increase, in percentage, in the last few years.
The studies on complexes of the octahedral d6 Ir(III) centre, for the most
part coordinated by cyclometalated ligands, of which the deprotonated
form of Hppy (2-phenylpyridine) can be considered a sort of archetype,
have suddenly expanded in recent years, either as mononuclear complexes,
or as a part of larger assemblies, or upon incorporation in polymers and
solid-state devices. Cyclometalated complexes of Ir(III) are by far the most
utilized class of ionic transition-metal complexes (iTMCs) light-emitting
electrochemical cells (LECs).5255
Emission wavelength tuning has been demonstrated through postcyclometallation modication of [Ir(mppy)3] (mppy=2-(4-methoxyphenyl)pyridine) at the aryl 5-position.56 Tuning has also been achieved by using a
substituted 2-phenylbenzothiazole,57,58 phenylimidazole59 and substitution in
[Ir(tolylpyridine)3]-based complexes.60 Complexes of the type [Ir(C6C6N)
-(C6N6N)] (C6C6N=pyridylbiphenylene, C6N6N=6-phenyl-2,2 0 -bpy)
have been prepared and showed a red-shifted emission spectra with respect to
the one of the previously reported bicyclometallated diphenylpyridine
complexes.61
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The inuence of halogen atoms on a homologous series of bis-cyclometalated Ir(III) complexes of general formula Ir(2,4-di-X-phenyl-pyridine)2(picolinate) (X=H, F, Cl, Br), have been studied showing that the
substituents have a strong impact on the optical properties of the complexes
with both electronic and geometric eects.62
Triplet state photophysics have been generated in two distinct diketopyrrolopyrrole (DPP) chromophores terminated with either phenyl or
thienyl spacers, when sandwiched between two Ir(III) complexes using
bipyridyl linkers. Low energy excitation of these metal complexes produced
strongly quenched singlet uorescence, generated quite intense, long-lived
(t=3 ms) absorption transients in the red and sensitized 1O2 photoluminescence in aerated solutions.63
Recent studies have revealed that many Ir(III) complexes possess high
structural diversity and rich photophysical properties that can be exploited
in the development of probes to determine biological structures and to
understand molecular recognition and cellular processes. In particular, it
has been established that water solubility, lipophilicity, cytotoxicity, cellular
uptake, and intracellular localization can all be tuned by using various
cyclometalating and polypyridine ligands.64
The eect of the position of aryl substituents in [Ir(Arpz)2(bpy)] (ArpzH=
1-arylpyrazole) has been investigated from a photophysical point of
view. The para position to the metal has an increased eect on emission
energy than that in the meta position.65 Enhanced luminescent emission
is observed in complexes of the formula [Ir(atz)2(tBu2bpy)] (atzH=4-aryl1,2,3-triazole, tBu2bpy=4,4 0 -bis-tert-butyl- 2,2 0 -bipyridyl) with quantum
yields that reach 80%.66
[Ir(bt)2(acac)] (bt=2-phenylbenzothiazole) acts as a ratiometric luminescent sensor for Hg(II) ions resulting in blue-shifted absorption and
emission.67 A carbazate complex [Ir(ppy)2(NH2NHCO2)] has been shown
to exhibit long luminescent lifetime and high quantum yield (t=1.8 ms,
f=0.45).68 Biscyclometalated iridium complexes with pyrene and perylene
appended acetylacetonate ligands undergo quenched 3MLCT emission
through triplettriplet energy transfer processes leading to long-lived 3IL
states.69 A complex containing two [Ir(ppy)2] moieties bridged by a 2,2 0 :
6 0 ,200 -terpyridyl-6,600 -dicarboxylate ligand shows intense luminescent emission (quantum yield of 18%, only 11% less than the mononuclear picolinate
analogue).70 Iridium complexes with two cyclometallated 1-aryl-3-methylimidazol-2-ylidene ligands and a pyrazolylpyridine-based ancillary ligandhave been investigated as complexes for OLED applications.71 Introduction
of phenyl substituents into the 6- and 6 0 -positions of the bpy ligand
in [Ir(ppy)2(bpy)] complexes allows the thermal population of the nonradiative 3MC states.72 [Ir(ppy)2(Me2SO)2]PF6 has been shown to be a
nucleus-specic turn-on luminescent staining agent for living cells.73 Complex
C exhibits extremely long-lived coumarin-centred 3IL states (75.5 ms) and
sensitizes DPA-based triplettriplet annihilation up-conversion.74 An Ir(III)
complex bearing a spiro-ring as pendant on a bpy ligand, undergoes
selective rhodamine spiro-ring opening in the presence of Hg(II) ions
resulting in modulation of energy transfer to iridium and increased emission
intensity.75
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The complex [Ir(tBu2bpy)(L)(NCS)], where L is a tripodal bis-cyclometalated triphenylphosphite ligand, is luminescent and when integrated in
OLED devices allows eciencies up to 14.1%.76 Ir(III) and Pt(II) cyclometalated complexes of oligothiophenylpyridines show a changeover from
3
LC/3MLCT phosphorescence to thiophene-based uorescence on going
from thiophenylpyridine to the bi- and trithiophenyl analogues.77 The tetranuclear complex in which two [Ir(ppy)2(CN)2] anions are bridged by two
[Ir(ppy)2] cations via the cyanide ligands retains the luminescent properties
of the mononuclear components with a phosphorescent quantum yield of
about 65%.78 An Ir(III)-based soft salt made by [Ir(dfppy)2(NCS)2] anions
and a dinuclear cation with two [Ir(dfppy)2] moieties bridged by a bis(imidazophenanthroline)carbozole ligand yields OLED devices with an
external eciency of 0.44.79 A complex with an [Ir(ppy)2(acac)] core and
phenylethynyl substituents in the pyridine 4-positions exhibits two-photon
absorption (TPA) at 800 nm with a TPA cross-section of 44 GM and
emission at 570 nm in toluene.80 A novel dinuclear Ir(II)Ir(II) dinitrogen
complex has been prepared and exhibits luminescent emission at 582 nm in
CH2Cl2 (f=2.5%).81
5

Platinum and gold

Platinum and gold coordination and organometallic compounds have a

large variety of photochemical properties, even larger than the probably
most investigated d6 metal complexes. Luminescent platinum compounds
are usually Pt(II) species, whereas the oxidation states of gold which can
give rise to luminescent species are Au(I), Au(II), and Au(III). Pt(II), Au
(III), and Au(I) share the property to be capable of forming luminescent
compounds exhibiting strong metal-metal interaction, a feature which is not
usually showed by d6 metal complexes.
[Pt(bpy)(1,2-benzenedithiolate)] complexes with a BODIPY chromophore attached to either the bpy or dithiolate ligand show neither BODIPYbased uorescence or Pt-based phosphorescent emission. Transient
absorption spectroscopy shows that BODIPY excitation results in singlet
energy transfer to the 1MLLCT state which then undergoes ISC to yield the
3
MLLCT. Population of the BODIPY 3LC then occurs through energy
transfer on the ps time scale and by a Dexter mechanism.82 A Pt(II) benzoporphyrin complex with four pendant BODIPY chromophores exhibits
fast singlet and triplet bidirectional energy transfer processes between
BODIPY and porphyrin units showing red phosphorescent at 722 nm, with a
quantum yield of 0.26.83 Cyclometalated dipyridylbenzene Pt(II) chloride
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complexes with CF3 pyridyl substituents are shown to result in red-shifted

excimer emission that reach the NIR region.84
The synthesis and the photophysical behavior of a Pt(II) terpyridyl perylenediimide (PDI) acetylide charge-transfer complex have been reported.
These studies revealed the spectroscopic characteristics of its associated
ligand-localized triplet state in both transient absorption and, for the rst
time, time-resolved step-scan FT-IR.85
Pt(II)acac complexes with benzothiazolylcoumarin,in which the coumarin
moiety is directly cycloplatinated, give triplet-triplet annihilation quantum
yields up to 15.4% in the presence of DPA.86 A Pt(II) chloride complex with a
cyclometalated 2,6-bis(N-alkylbenzimidazol-2-yl)benzene ligand exhibits
bright green luminescence (500587 nm, t=5.3 ms, f=0.19) and OLED
devices with an eciency of 11.5%.87 [(tBu3tpy)Pt(CRCtpy)PtCRCtBu](OTf)2 exhibits unusually higher emission quantum yield in CH2Cl2
(f=0.43) than in MeCN (less than 10%) attributed to the formation of an
excited state contact ion pair in CH2Cl2 solutions.88 A [Pt(ppy)(acac)]
complex with dimesitylboron electron-transporting group attached to
pyridine and naphthanlenylphenylamine hole-transporting group appended
to phenyl yields bright orange OLED devices with eciencies up to 10.6%.89
Cyclometalated Pt(II) 2,6-bis(oxazol)phenyl complexes are moderately
emissive with easy tuning of emission wavelength available through
the oxazole moieties.90 Binuclear complexes [{Pt(Me)(L)}2(m-dppm)] (L=ppy
or benzo[h]quinoline, dppm=(diphenylphosphine)methane) show intense
orange-red emission stemming from 3MMLCT excited states.91 1,3-bis(2-pyridylimino)isoindoline Pt(II) complexes with monodentate N-donors
such as pyridine, phthalazine or phenanthridine show orange-red emission
from 3IL states mixed with some 3MLCT character.92
The DFT calculations performed and the luminescence measurements on
a series of tetranuclear gold(I) uorinated amidinate complexes of general
formula [Au(ArN)2C(H)]4 (Ar=4-FC6H4; 3,5-F2C6H3; 2,4,6-F3C6H2;
2,3,5,6-F4C6H), elucidated the eect of the uorine number on the properties of this kind of species. In particular, it has been showed that the less
uorinated amidinate complexes display structured emission.This behaviour is due to metal-perturbed intraligand transitions with a low inuence
from the Au(I) centers. However, the higher metal contribution to the
frontier orbitals of the more uorinated complexes leads to highly metalperturbed unstructured LMCT emissions.93
Binuclear complexes with two [Pt(PEt3)2(CRCPh)] moieties bridged by a
pentacenyl-6,13-diacetylide unit show ligand uorescence in the NIR
spectral region (710730 nm).94 The complex [Pt(acac)(C6N)] (C6N is a
cyclometalated 4-pyrazolylnaphthalimide ligand) yields a triplettriplet
annihilation up-conversion eciency of 14.1% with DPA.95 The complex
[Pt(N6C6N)Cl] (N6C6N=N-phenyl-N-(3-(pyridin-2-yl)phenyl)pyridin2-amine) has improved square-planar geometry compared to the dipyridylbenzene analogue and is intensely luminescent (f=0.65).96 Increased
electronic insulation between metal and photochromic dithienylethene
moieties in a series of Pt(II) tpy complexes with dithienylethene-functionalised acetylide ligands has been shown to reduce the rate of MLCT sensitized ring closure and promotes Pt(tpy)-based phosphorescent emission.97
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Arylacetylide complexes of the form [Pt(C C)(CCAr)2], where C6C

is the chelating carbene 1,10-dipentyl-3,30-methylene-diimidazol-2,20-diylidene, display emission from 3IL/3MLCT mixed states.98 [Pt(tpy)Cl] complexes with 9,9-di(2-ethylhexyl)-7-diphenylaminouoren-2-yl substituents
in the tpy 4-position exhibit TPA (Two Photon Absorption) Z-scanderived cross sections of 6002000 GM.99 The complex [{Pt(C6N6N)}2(mP-Fc-P)]2 (C6N6N=4-tolyl-6-phenyl-2,20-bipyridine, P-Fc-P=1,10-bis(diphenylphosphino)ferrocene) undergoes PET from ferrocene to Pt with a
constant rate of 2  106 s1 yielding a charge separated state living 9.4 ms.100
D

Bisacetylide complexes (D) with electron donating substituents (in the

place of R in D) have triplet excitons localised away from the Pt centre,
resulting in red-shifted spectra and prolongated triplet state lifetime with
the opposite true with inclusion of donating groups. The rate of ISC and the
S1-T1 energy gap show for the Marcus relation a reorganisation energy of
0.83 eV.101
The emission quantum yields and the lifetimes of a series of alkynyl gold
derivatives with general formulae [(diphos)(AuCCpy)2] (diphosphane
=2,2 0 -bis(diphenylphosphanyl)propane) have shown a correlation with the
Au(I)    Au(I) distance. The analysis of the experimental results demonstrated the existence of a correlation between Au(I) . . . Au(I) distance and the
radiative rate constant for the deactivation of the emissive triplet states.102
A series of gold(III) complexes containing various tridentate cyclometalating ligands derived from 6-phenyl-2,2 0 -bipyridine and alkynyl ligands has
been reported to be luminescent at 77 K from an intraligand excited state with
some charge transfer character from the aryl to the bipyridine moiety.103
A cluster with the formula [Au6(C)Cu2(dppy)6]4 (dppy= 2-(diphenylphosphino)-pyridine) with an unprecedented trigonal prismatic Au6 core
containing a hypervalent C-atom has been reported. The cluster exhibits
bright red luminescent emission.104
A reported gold(III) complex of a tris(pentauorophenyl)corrole
ligand brominated at each b-pyrrole position exhibits emission in
solution at RT (l=769 nm, t=195 ps, f=0.003).105 A series of highly
luminescent octanuclear Au(I)/Cu(I) clusters with the formula
[Au6Cu2(CRCR)6(P6P)2]2 (P6P=1,4-bis(diphenylphosphino)benzene) has
been reported. When R=1-cyclohexanolyl emission at 488 nm (quantum
yield=94%) is observed.106 Gold(I) complexes containing oligo(o- or mphenyleneethynylene) ligands exhibit emission attributed to a short-lived
prompt emission and a long-lived delayed emission.107 A series of Cu/Au
systems of the form {[Au(C6X5)2][Cu(NCR)(m2-C4H4N2)]}n (X=F, Cl;
R=Me, Ph, CHCHPh) is brightly luminescent when R is Me or Ph
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stemming from a pyrimidine-localised MLCT state, whereas the styrenyl

substituent results in non-radiative decay from a nitrile ligand based MLCT
state.108 Cyclometalated gold(III) complexes of the type [(C6N)Au(CCR)2]
have been reported (C6N=ppy, dfppy, 2-(thien-2-yl)pyridine, benzoquinoline, phenylisoquinoline; R = aryl, silyl groups). Emission occurs from
metal perturbed C6N 3IL states allowing emission tuning on the basis of the
identity of C6N.109,110 Organodiselone Au(I)-Tl(I) complexes are luminescent in the solid state and at 77 K with lifetimes in the ns range. The
emissive state is an admixture of 3MMLCT and 3LC states.111 Tetra- and
octanuclear dendritic-like arylthiolate gold(I) complexes around an oligophosphino core display mainly 3LMCT based emission with F-, MeO- and
Me-4-aryl substituents and 3LC emission in the presence of NO2
substituents.112 An 8-hydroxyquinoline-funtionalized rhodamine-based
receptor acts as a reversible uorescent sensor for gold(III) ions with high
selectivity and has been used for imaging of gold(III) in living cells.113
6

Copper

Copper in solution has two common oxidation states: 1 and 2. Due to

their intrinsically superior photochemical and photophysical properties,
herein our attention is focused on Cu(I) complexes. Anionic Cu(I) complexes do not exhibit attractive photophysical properties (e.g., luminescence), unlike cluster and cationic complexes which show a very rich
photophysical behaviour. Among the latter, the most extensively investigated are NN-type (where NN indicates a chelating polypyridine-like
ligand, typically 1,10-phenanthroline) or PP-type (where PP indicates a
bisphosphine ligand). Both homoleptic [Cu(NN)2] and heteroleptic
[Cu(NN)(PP)] compounds have been investigated.
The emissive states are assigned as mixtures of 3ILCT and 3MLCT or
3
LLCT and3MLCT.114 The complex [Ir(ppy)2(L)] (L is a dipicolylaminomethyl-appended 2-(benzothienyl)pyridine ligand) acts as a ratiometric
sensor for Cu2 under physiological conditions.115 DSSC devices prepared
using Cu(I) complexes with bpy ligands functionalized at the 6-position
with furyl, thienyl, methylpyrrolyl, phenyl and methyl substituents exhibit
eciencies approaching 1.5% (versus 4.5% for N719).116 Neutral Cu(I)
complexes such as [Cu(Hqbm)(PPh3)2] (Hbqm=2-(20-quinolyl)- benzimidazole), exhibit blue-shifted phosphorescent emission that is longer-lived
than their cationic counterparts, such as [Cu(qbm)(PPh3)2]+, attributed to
additional LC transitions besides MLCT transitions.117 [Cu(N6N)(P6P)]
complexes (N6N=bpy or phen, P6P=pop or dppb) yield light emitting
electrochemical cells with eciencies approaching those based on Ru(II)
and Ir(III) complexes.118 The species E has been reported as a selective twophoton uorescent probe for Cu(I) ions and has been used to image Cu(I) in
live cells using two-photon uorescence microscopy.119 A Cu(II) complex
with a tridentate dansyl-functionalized ligand acts as a turn-on uorescent
sensor for nitric oxide.120 A sensor comprising a tricarbocyanine receptor
and a 2,20-azanediyl bis(N-hydroxyacetamide) NIR uorophore gives a
10-fold enhancement in NIR emission in the presence of Cu2 ions and has
been applied in live cell imaging.121
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Recently the prototype [Cu(CN-xylyl)2(dmp)]tfpb (dmp=2,9-dimethyl-1,10phenanthroline; CN-xylyl=2,6-dimethylphenylisocyanide; tfpb=tetrakis(bis-3,5-triuoromethylphenylborate)), having a millisecond emission
lifetime, has been reported to be at least 40 times more sensitive to dioxygen,
with respect to [Ru(phen)3]tfpb2 (phen=1,10-phenanthroline).122 Polypyridyl Cu(I) complexes have also being considered as a replacement for
ruthenium complex sensitizers in dye-sensitized solar cells, owing to their
striking similarities in absorption spectra and photophysics. Photoinduced
charge-transfer dynamics from a Cu(I) diimine complex to TiO2 nanoparticles were investigated by combining multiple time-resolved spectroscopic methods. An ecient and ultrafast electron transfer process from the
singlet MLCT state was discovered as a result of structural control owing to
the attening of the tetrahedral geometry in the complex and the bulky
groups in the ligands.123
7

Lanthanides

The lanthanides 3 centeres (Ln(III)) exhibit the most external electronic

conguration with fn orbitals, n=1 to 14. The Ln(III) centeres become
luminescent only upon inclusion in Ln-antenna complexes, obtained by
saturation of 89 positions around the metal ion. Several reviews are
available on the photophysics of this quite large family of complexes.
The mechanism of non-overlapping FRET (nFRET) (where energy
transfer is observed between a spectrally non-overlapping donor emitter and
an acceptor absorber) has been investigated using an europium chelate
emitter and an organic uorophore separated by an oligonucleotide. From
distance and temperature dependent data the mechanism is proposed to
proceed through thermal excitation from the lowest Eu emission state to a
higher ionic or LMCT state.124
The sensitisation of lanthanide-based emission and energy transfer in
mixed transition metal/lanthanide assemblies remains an active area with a
number of reports appearing in the literature.125130 Tb(III) complexes
with octadentate bis(diaminethane) capped ligands containing four 2hydroxyisonaphthalamide chelate groups have been investigated as new
luminescent lanthanide standards and show high quantum yields and long
lifetimes in water (ftot more than 50%, t>2.45 ms).131 A water
soluble Yb(III) rhodamine-appended porphyrin complex capped with a
[CpCo{(MeO)2P=O}3] anion exhibits TPA and impressive NIR emission
(1060 nm, f=2.5%).132 The complex [Tb(deppa)3] (deppa=6-(diethoxyphosphoryl)picolinate) exhibits emission at 545 nm (f=0.4) with a lifetime
of 2.4 ms.133 An Eu(III)/ferrocene dyad exhibits reversible switching of
Eu(III) luminescent emission.134
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Luminescent [Ln(Tf2N)3]complexes in a [1-butyl-3-methylpyrrolidinium][Tf2N] ionic liquid (Tf2N =bis(triuoromethyl-sulfonyl)amide) display remarkably long lifetimes compared to values quoted for Ln(III)
complexes in solution due to weak vibrational quenching.135 Europium and
terbium tris(hfac) (hfac=1,1,1,5,5,5-hexauoropentane-2,4-dione) complexes with chiral bis(oxazole)pyridine (pybox) ligands display circularly
polarised luminescent (CPL) emission. Despite having the same chirality,phenyl-substituted pybox ligands result in opposite CPL spectra to
those of Me- and iPr-substituted complexes.136 Dimeric lanthanide (Eu, Gd,
Tb) complexes with bridging biphenyl or diphenylmethane bridges give
enhanced luminescent emission for imaging in the presence of human serum
albumin.137
Arylphosphonate-decorated complexes of Tb(III) are emissive with
quantum yields between 0.18 and 0.24 and lifetimes of about 43 ms.138
Nd(III), Yb(III) and Eu(III) complexes of ligands decorated with 8aminoquinoline and anthraquinone uorophores display dual emission
properties that are tuned in the presence of dierent metal ions.139
F

Complex F is brightly luminescent in water (f=0.13, t=1.8 ms) but

displays poor two photon absorption coecients. Introduction of 4-arylacetylene substituents on the pendant pyridyl rings reduces the luminescent
intensity but yield a TPA cross-section of 45 GM at 720 nm.140 Eu(III)
complexes with uorenyl-acac ligands with phenyl, 2-naphthyl or 4-biphenyl substituents allow tuning of the excitation wavelength. Replacement of
phenyl by naphthyl or biphenyl signicantly shifts excitation into the visible
(ca. 500 nm) with quantum yields between 19 and 43% inthe solid state,
amongst the highest reported for a visible wavelength sensitised Eu(III)
complex.141
Lanthanide complexes of a 2,6-bis(pyrazolyl)pyridine ligand functionalized with two iminobismethylenephosphate groups are stable in biological
media and are luminescent with very long lifetimes (t=1.50 and 3.28ms for
Eu and Tb respectively). Lanthanide complexes based on bis(amide)derivatives of diethylenetriaminepentaacetic acid with thiol functionalities
allow access to heterobimetallic complexes through disulphide bridge formation. The Eu/Tb complex exhibits dual colour ff emission from both
Eu and Tb centres but with some energy transfer from Tb(III) to Eu(III).142
An 8-hydroxyquinoline ligand substituted with a BODIPY group at the
5-position has been used for the enhancing of NIR emission from Yb(III),
Er(III) and Nd(III). Nd(III) and Er(III) complexes emit weakly at 1060 and
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1382 nm respectively whereas the Yb(III) complex emits strongly at 976 and
1003 nm.143
Tris(thienoyltriuoroacetonato) Eu(III) complexes with 4,7-disubstituted
phen ligands have been investigated by DFT/TDDFT methods. Calculations reveal that the luminescent 5D0 state can be populated for H, Me,
OMe, Cl and Br substituents but not for p-conjugating CO2Et and
C4H3OMe groups through tuning of the energy of the excited triplet
state.144 A terpyridinetetraacetate Eu(III) complex connected to an ampicillin moiety is able to bind b-lactamase. The long lifetime of the emissive
Eu(III) sensor (41.25 ms) has been exploited for time-gated multicolour
bioimaging applications.145 A related complex with a pendant 3,4diaminophenoxy group acts as a light-switch-on time-gated imaging probe
for NO which reacts with the diaminophenyl group to form a benzotriazole
moiety.146
In 2012 the photophysical properties of a series of lanthanoid cryptates
(Eu and Tb) with an increasing number of 2,2 0 -bipyridine units have been
investigated in aqueous solution. The results showed that increasing the
number of bipyridine units in the cryptates ions both an increase in the
energy of the rst excited singlet state S1 and a lowering of the T1 triplet
energy levels is observed.147,148
G

With the goal to prepare new sensitizers for lanthanoids, a new

multidentate ligand (G) has been reported to sensitize both visible and
near-infrared (NIR) emitters by using the same excitation wavelength, with
signicantly high quantum yields. In particular a new holmium luminescent
complex was described to emit in both the visible and NIR region.149
A divalent Eu(II) complex exhibits luminescent emission at 528 nm
which can be attributed to a 4f-5d transition and is a rare example of the
photophysical study of a Eu(II) complex.150 Dinuclear complexes containing two Ln(hfac)3 moieties bridged by two m-phenolic hydroxyquinoline
ligands display uoride ion induced luminescent enhancement through
replacement of H2O ligands or formation of OH-F hydrogen bonds that
suppress non-radiative O-H oscillators.151 Lanthanide nitrate complexes of
the oligoimidazole ligands bis- and tris{[2-{(imidazol-4-yl)methylidene}amino]ethyl}amine show enhancement of Ln(III) phosphorescence due to
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152

high ligand triplet state energies. Remarkable Nd(III) and Yb(III) containing clusters where the Ln(III) ions are surrounded by a complex array of
three metallacrown structures comprising 16 Zn(II) ions and 16 picolinehydroxamic acid ligands have been reported. These new structures exhibit
NIR emission.153
An Eu(III) cyclen-based complex with a 4,7-diphenyl-1,10-phenanthroline-disulfonate (BPS) antenna ligand acts as a turn-o luminescent sensor
for transition metal ions through BPS displacement. A detection limit of
emission quenching by Fe(II) ions of about 10 pM was observed.154,155
Eu(III) and Sm(III) trigonal dodecahedral complexes with chelating
bis(phoshineoxide) ligands such as 4,5-bis(diphenylphosphoryl)-9,9-dimethylxanthene and hfac ligands display markedly high emission quantum
yield (Eu, f=5572%; Sm, f=2.45.0% in d6-acetone) due to enhancement of the electric dipole transition and suppression of vibrational
relaxation.156
8

Miscellanea

A conjugate of a N,N-bis(2-phenylthioethyl)amine binding domain and a

1,2-dihydroxyanthraquinone uorophore is a selective and sensitive sensor
for Al(III) ions through switching o of uorescence-quenching PET processes on Al3 binding.157 Al(III) complexes of a tetraiodinated corrole
ligand exhibit deep red emission (612 to 700 nm) from a long-lived triplet
excited state (t=92 ms in degassed toluene).158 The eects of the presence of
both electron-donating and electron-withdrawing 8-hydroxyquinolate (q)
ligand substituents on the photophysical properties of their Alq3 complexes
have been investigated. High OLED eciencies of up to 4.6% were
observed using these uorophores.159 The tris-homoleptic Al(III) complex
of the fused-ring hydroxyquinolate ligand 11H-indolo[3,2-c]quinolin-4-ol
exhibits deep blue luminescent emission and three times the uorescent
quantum yield compared to the parent Alq3.160 A series of stable
indium bacteriochlorins has been prepared and shows NIR absorption
(740780 nm).161 Fluorescent indium and gallium bis(thiosemicarbazonate)
complexes have been investigated as confocal luminescent imaging
agents.162 A series of pyrrolyldipyrrinato tin(IV) complexes shows uorescent quantum yields between 0.28 and 0.61.163 Cyclen-functionalised
perylenediimides have been reported to act as selective and highly sensitive
uorescent probes for lead(II) ions and can be used for imaging of Pb(II) in
living cells.164
Complexes of the type trans-[M(cyclam)(CCCF3)2]OTf (where
M=Cr3, Co3, and Rh3; OTf=triuoromethanesulfonate) were prepared and in the case of the rhodium complex the triuoropropynyl ligand
enhances the MC luminescence to a quantum yield greater than 0.1.165
The rhodamine B based ligand precursor N-(3 0 ,6 0 -Bis(diethylamino)-3oxospiro-[isoindoline-1,9 0 -xanthene]-2-yl)picolinamide is a light switch-on
sensor for Fe(III) that could be used as intracellular uorescent imaging
agent.166 An organic assembly based on BODIPY, cyanine uorophores
and a terpyridyl metal binding domain acts as a sensor for Fe(II) ions.
On iron binding, MLCT state quenches cyanine emission whilst
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leaves BODIPY emission unchanged.

Clusters with the formula
[Mo6X8(n-C3F7CO2)6]2 where X is Br or I show extraordinarily bright
long-lived red luminescence with f=0.23 and 0.36 respectively and t=370
and 303 ms respectively.168
The hexauorophosphate salt of the cationic dyad 5-{4-[Re(CO)3(picoline)-(4-methyl-2,2 0 -bipyridyl-4 0 -carboxamidyl)]phenyl}-10,15,20-triphenylporphyrinatopalladium(II)photoreduces CO2 to CO. Time-resolved
studies show a multistep energy transfer from Pd to porphyrin and nally
to Re as energy trap.169 Tetranuclear assemblies of the form
[{(phen)2M(dpp)}2Ru{(dpp)PtCl2}]6 (M=Ru, Os, dpp=dipyridylpyrazine) exhibit terminal metal to dpp 3MLCT transition. Emission from
these states undergoes quenching by population of triplet charge transfer
states centred on the dpp ligand bridging to Pt.170
Temperature-dependent excited state equilibria have been directly
observed between 3MLCT states and 3LC states in dinuclear complexes
containing [Ru(tpy)2] units spaced by conjugated electron-poor bridges.171
Dyads of the form [(bpy)2-Ru(dpdpz)Pt(CRCAr)2]2 (dpdpz=2,3-di(pyrid2-yl)-5,6-diphenylpyrazine), in which the Pt(II) centre is cyclometalated to
dpdpz, exhibit intense visible and NIR mixed Ru- and Pt-based MLCT
absorption and NIR emission.172 Ru(bpy)2/Ru(bpy)2 and Ru(bpy)2/
Os(bpy)2 bimetallic complexes bridged by 4,5-(benzimidazol-2-yl)imidazolate show MLCT-based phosphorescence; moreover energy transfer from
Ru to Os is observed in the heterobimetallic complex.173 An Ir(III)/Pt(II)
triad displays red-shifted luminescent emission compared to both the
mononuclear Ir(III) bis-cyclometalated and Pt(II) mono-cyclometalated
component analogues such that the metallic units do not retain their individual photophysical properties.174 Multinuclear platinum(II) acetylide
complexes containing triethynylbenzene or 1,4-bis(3,5-diethynylphenyl)buta-1,3-diyne cores show TPA induced luminescence and TPA cross
sections from 6 to 191 GM upon excitation at 720 nm.175,176
The synthesis, characterization, photophysics, and time-dependent densityfunctional theory (TD-DFT) calculations of spirobiuorene-bipyridine
based Ir(III), Os(II), and mixed Ir/Os complexes have been presented. The
results clearly show that the ligand uorescence is almost quantitatively
quenched in all the mono- and bimetallic systems at both temperatures and
ecient energy transfer toward the appended metal chromophores is
operative.177
The synthesis of p-bonded ruthenium, rhodium, and iridium o-benzoquinones of the general formula [M(L)2(OM 0 -linker)][X]n (n=0, 1, 2) where
M=Ru, L=bpy and M 0 =Rh, Ir, L=ppy. In these binuclear compounds,
the luminophore brick adopts a distorted octahedral geometry due to the
two polypyridine ligands and to cis O6O coordination of the OM-linkers.
The emission properties recorded at low temperature show a red-shifted
emission compared to those of the parent [M(L-L)3] (M=Ru, Rh, Ir)
compounds with polypyridine or phenylpyridine ligands.178
A hexakis(zinc(II)porphyrin) nano-ring with butadiynyl inter-porphyrin
linkers has been prepared. Light absorption generates an excited state
delocalized over the whole p-system with a lifetime of 0.5 ps.179 A zinc
porphyrin dye with a cobalt-based electrolyte has been used to assembly
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DSSC devices obtaining the greatest eciencies to date (up to 13.1%).180

Tetra-meso-arylporphyrinatozinc polyimide containing dendrons built on a
dimethylxanthenebis(M(II)porphyrin) core (M=Cu, Zn) have been investigated. The dendrons can act as singlet and triplet energy acceptors or
donors depending on the individual dendrimeric system.181
Cyclic bis-zincporphyrin forms host-guest inclusion complexes with C60
and C70 fullerenes. These exhibit an excited state involving electron transfer
to fullerene which decays to the ground state over several hundred picoseconds.182 Picosecond TA spectroscopy reveals that excitation in the Soret
band of tetraphenylporphyrinzinc(II) (ZnTPP) in the presence of excess C60
results in the formation of a relatively long-lived charge separated state.183
A diethylpyrrole-bridge dizincporphyrin is able to interact with pyrene.
Fluorescence studies show photoinduced singlet-singlet energy transfer
from excited pyrene to Zn.184 Assemblies containing two zinc phthalocianines (ZnPc) bridged by an imidazole-functionalized perylenediimide unit
display CS states with lifetimes between 3 and 9.8 ns.185 Photoinduced
energy transfer between noncovalent complexes of ZnPc and C60 pyrrolidine tris-acid ethyl ester (PyC60) occurs predominantly by energy transfer
from a PyC60 triplet excited state to ZnPc.186 A distorted fused porphyrinphthalocyanine conjugate ZnPZnPc has been reported. In the presence of
pyridylfullerene, excitation results in energy transfer from ZnP to ZnPc
followed by electron transfer to fullerene to generate a CS state, which
deactivates to the ground state in about 1.5 ns.187 A conjugate, two C60
fullerenes appended to a ZnP moiety by 1,2,3-triazole linkers, exhibits PET
and a long-lived charge-separated state (t=0.48 ms) in benzonitrile. In
toluene, intramolecular energy transfer occurs resulting in C60 triplet state
generation on ZnP excitation.188
A crown-BODIPY-ZnP assembly acts as a receptor for alkyl ammonium
functionalized C60. Excitation of the BODIPY moiety results in singlet
energy transfer to ZnP occurring in 7 ps. Following electron transfer processes result in the formation of the charge separated state which has a
lifetime approaching 100 ms, the longest reported for a system of this
type.189 A supramolecular array comprising a tetrakispyridine substituted
perylenebisdiimide acceptor coordinated to four Ru(II) carbonyl phthalocyanine (RuPc) donor moieties has been reported. Excitation of either the
donor or acceptor groups results in formation of a radical ion pair state with
a lifetime of several hundred ps in toluene.190 RuPc and Ru naphthalocyanines with dendronised axial pyridine ligands show optical power limiting properties.191 Supramolecular arrays based on Sn(IV) porphyrin
coordinated to a Ru(II) carbonyl porphyrin with two expanded thiaporphyrins coordinated axially to Sn have been reported. Photophysical studies
show little coupling between components showing that they retain their
individual features.
Sn-based emission is signicantly reduced, however, due to non-radiative
decay pathways operating in these systems.192 In contrast to the
non-luminescent Ni(II) complex, Pd(II) and Pt(II) complexes of
1,4,8,11,15,18,22,25-octabutoxyphthalocyanine exhibit deep red uorescent
and NIR phosphorescent emission from singlet and triplet excited states
respectively.193 Water-soluble Pt and Pd phthalocyanine complexes have
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been shown to sensitize singlet-oxygen formation with a quantum yield of

0.24.194 A multinuclear porphyrin (P) array based on an Au(III)P core
surrounded by four free-base (fb) P units and 12 ZnP units at the periphery
has been obtained through click chemistry. Excitation of ZnP results in
energy transfer to fbP and in turn charge transfer to Au(III)P. The resultant
charge-shift state lives for microseconds at room temperature.195
Mixed porphyrin/phthalocyanine double-decker rare-earth complexes of Y(III), Sm(III), Eu(III), Tb(III), Dy(III), and Lu(III) have been
developed as broad band light absorbers and electron donors in
bulk heterojunction solar cells. Eciencies of up to 0.82% have been
achieved.196
9

Abbreviations

BL
CS
CT
DFT
DSSC
GM
HOMO
IL
ILCT
ISC
LC
LEC
LLCT
LMCT
LMMCT
LUMO
MLCT
MLLCT
MMLCT
MC
MLCT
NIR
OLED
QD
TDDFT
Acac
bpy
tpy or terpy
dppz
phen
pic
ppy
ppz
tppz

Bridging Ligand
Charge Separation/Separated
Charge Transfer
Density Functional Theory
Dye Sensitized Solar Cells
two-photon absorption cross section units (GoeppertMayer unit)
Highest Occupied Molecular Orbital
Intraligand
Intraligand Charge Transfer
intersystem crossing
Ligand Centred (pp*)
Light Emitting Cells
Ligand-to-Ligand Charge Transfer
Ligand to metal charge transfer
Ligand to metal to metal charge transfer
Lowest Unoccupied Molecular Orbital
Metal to ligand charge transfer
Metal to ligand to ligand charge transfer
Metal to metal to ligand charge transfer
Metal Centred (dd)
Metal-to-Ligand Charge Transfer
Near Infrared
Organic Light Emitting Diode
Quantum Dot
Time Dependent Density Functional Theory
monoanion of acetyl acetone
2,2 0 -bipyridine
2,2 0 ;6 0 ,2 0 -terpyridine
dipyrido[3,2-a:2 0 ,3 0 -c:]phenazine
1,10-phenathroline
monoanion of 2-picolinic acid
(anion of) 2-phenylpyridine
(anion of) phenylpyrazole
tetrakis(2-pyridyl)pyrazine
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References
1 Paul I. P. Elliott, Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem., 2012, 108,
389407.
2 V. W.-W. Yam and K. M.-C. Wong, Chem. Commun., 2011, 47, 1157911592.
3 Coord. Chem. Rev., 2011, 255(2122).
4 A. Reynal and E. Palomares, Eur. J. Inorg. Chem., 2011, 4509.
5 G. Zhou, W.-Y. Wong and X. Yang, Chem.Asian J., 2011, 6, 1706.
6 P. S. Wagenknecht and P. C. Ford, Coord. Chem. Rev., 2011, 255, 591.
7 R. Bakova, M. Chergui, C. Daniel, A. Vlcek, Jr and S. Zalis, Coord. Chem.
Rev., 2011, 255, 975.
8 Q. Zhao, C. Huang and F. Li, Chem. Soc. Rev., 2011, 40, 2508.
9 K. K.-W. Lo, S. P.-Y. Li and K. Y. Zhang, New J. Chem., 2011, 35, 265.
10 G.-J. Zhou and W.-Y. Wong, Chem. Soc. Rev., 2011, 40, 2541.
11 V. W.-W. Yam and K. M.-C. Wong, Chem. Commun., 2011, 47, 11579.
12 J. F. Zhang, Y. Zhou, J. Yoon and J. S. Kim, Chem. Soc. Rev., 2011, 40, 3416.
13 O. S. Wenger, Chem.Eur. J., 2011, 17, 11692.
14 X. He and V. W.-W. Yam, Coord. Chem. Rev., 2011, 255, 2111.
15 D.-L. Ma, V. P.-Y. Ma, D. S.-H. Chan, K.-H. Leung, H.-Z. He and
C.-H. Leung, Coord. Chem. Rev., 2012, 256(2324), 30873113.
16 G. La Ganga, F. Puntoriero, S. Campagna, I. Bazzan, S. Berardi, M. Bonchio,
A. Sartorel, M. Natali and F. Scandola, Faraday Discuss., 2012, 155, 177190.
17 S. Berardi, G. La Ganga, M. Natali, I. Bazzan, F. Puntoriero, A. Sartorel,
F. Scandola, S. Campagna and M. Bonchio, J. Am. Chem. Soc., 2012, 134(27),
1110411107.
18 M. Natali, M. Orlandi, S. Berardi, S. Campagna, M. Bonchio, A. Sartorel and
F. Scandola, Inorg. Chem., 2012, 51(13), 73247331.
19 J. A. Stull, R. D. Britt, J. L. McHale, F. J. Knorr, S. V. Lymar and J. K. Hurst,
J. Am. Chem. Soc., 2012, 134, 1997319976.
20 D. Moonshiram, J. W. Jurss, J. J. Concepcion, T. Zakharova, I. Alperovich,
T. J. Meyer and Y. Pushkar, J. Am. Chem. Soc., 2012, 134, 46254636.
21 M. B. Majewski, N. R. de Tacconi, F. M. MacDonnell and M. O. Wolf, Inorg.
Chem., 2011, 50, 9939.
22 H. Ahmad, A. J. H. M. Meijer and J. A. Thomas, Chem. Asian J., 2011, 6,
2339.
23 V. L. Gunderson, E. Krieg, M. T. Vagnini, M. A. Iron, B. Rybtchinski and
M. R. Wasielewski, J. Phys. Chem. B, 2011, 115, 7533.
24 S. Ji, H. Guo, W. Wu, W. Wu and J. Zhao, Angew. Chem., Int. Ed., 2011, 50,
8283.
25 M. Four, D. Riehl, O. Mongin, M. Blanchard-Desce, L. M. Lawson-Daku,
J. Moreau, J. Chauvin, J. A. Delaire and G. Lemercier, Phys. Chem. Chem.
Phys., 2011, 13, 17304.
26 H. Ahmad, A. J. H. M. Meijer and J. A. Thomas, Chem.Asian J., 2011, 6,
2339.
27 D. G. Brown, Nawaporn Sanguantrakun, Benjamin Schulze, Ulrich
S. Schubert and Curtis P. Berlinguette, J. Am. Chem. Soc., 2012, 134(30),
1235412357.
28 M. Guel, F. Puntoriero, S. Serroni and G. Denti, Eur. J. Inorg. Chem., 2011,
709720.
29 L. Wang, W.-W. Yang, R.-H. Zheng, Q. Shi, Y.-W. Zhong and J. Yao, Inorg.
Chem., 2011, 50, 7074.
30 A. Baron, C. Herrero, A. Quaranta, M.-F. Charlot, W. Leibl, B. Vauzeilles
and A. Aukauloo, Chem. Commun., 2011, 47, 11011.

174 | Photochemistry, 2013, 41, 156181

Downloaded by University of Lancaster on 17/01/2015 22:23:30.

Published on 31 October 2013 on http://pubs.rsc.org | doi:10.1039/9781849737722-00156

View Online

31 T. Irebo, M.-T. Zhang, T. F. Markle, A. M. Scott and L. Hammarstrom,

J. Am. Chem. Soc., 2012, 134(39), 1624716254.
32 K. C. D. Robson, B. D. Koivisto, A. Yella, B. Sporinova, M. K. Nazeeruddin,
T. Baumgartner, M. Graetzel and C. P. Berlinguette, Inorg. Chem., 2011, 50,
5494.
33 P. G. Bomben, T. J. Gordon, E. Schott and C. P. Berlinguette, Angew. Chem.,
Int. Ed., 2011, 50, 10682.
34 W.-S. Han, J.-K. Han, H.-Y. Kim, M. J. Choi, Y.-S. Kang, C. Pac and
S. O. Kang, Inorg. Chem., 2011, 50, 3271.
35 I. Stengel, A. Mishra, N. Pootrakulchote, S.-J. Moon, S. M. Zakeeruddin,
M. Graetzel and P. Baeuerle, J. Mater. Chem., 2011, 21, 3726.
36 W. B. Heuer, H.-L. Xia, W. Ward, Z. Zhou, W. H. Pearson, M. A. Siegler,
A. A. Narducci Sarjeant, M. Abrahamsson and G. J. Meyer, Inorg. Chem.,
2012, 51(7), 39813988.
37 E. N. Dixon, M. Z. Snow, J. L. Bon, A. M. Whitehurst, B. A. DeGra,
C. Trindle and J. N. Demas, Inorg. Chem., 2012, 51(6), 33553365.
38 J. Su, L. Shi, X. Sun, W. Guan and Z. Wu, Dalton Trans., 2011, 40, 11131.
39 L.-H. Chung, S.-C. Chan, W.-C. Lee and C.-Y. Wong, Inorg. Chem., 2012,
51(16), 86938703.
40 C.-C. Hsu, C.-C. Lin, P.-T. Chou, C.-H. Lai, C.-W. Hsu, C.-H. Lin and
Y. Chi, J. Am. Chem. Soc., 2012, 134(18), 77157724.
41 E. Trovato, M. L. Di Pietro and F. Puntoriero, Eur. J. Inorg. Chem., 2012
39843988.
42 R. D. Costa, D. Tordera, E. Orti, H. J. Bolink, J. Schonle, S. Graber,
C. E. Housecroft, E. C. Constable and J. A. Zampese, J. Mater. Chem., 2011,
21, 1610816118.
43 T. M. McLean, J. L. Moody, M. R. Waterland and S. G. Telfer, Inorg. Chem.,
2012, 51(1), 44655.
44 M.-W. Louie, T. T.-H. Fong and K. K.-W. Lo, Inorg. Chem., 2011, 50(19),
94659471.
45 B. S. Uppal, R. K. Booth, N. Ali, C. Lockwood, C. R. Rice and P. I. P. Elliott,
Dalton Trans., 2011, 40, 7610.
46 A. El Nahhas, C. Consani, A. M. Blanco-Rodriguez, K. M. Lancaster,
O. Braem, A. Cannizzo, M. Towrie, I. P. Clark, S. Zalis, M. Chergui and
A. Vlcek, Jr, Inorg. Chem., 2011, 50, 2932.
47 T. Yoshimura, S. Ishizaka, T. Kashiwa, A. Ito, E. Sakuda, A. Shinohara and
N. Kitamura, Inorg. Chem., 2011, 50, 9918.
48 A. W.-Y. Cheung, L. T.-L. Lo, C.-C. Ko and S.-M. Yiu, Inorg. Chem., 2011,
50, 4798.
49 M. V. Werrett, D. Chartrand, J. D. Gale, G. S. Hanan, J. G. MacLellan,
M. Massi, S. Muzzioli, P. Raiteri, B. W. Skelton, M. Silberstein and S. Stagni,
Inorg. Chem., 2011, 50, 1229.
50 L. A. Casson, S. Muzzioli, P. Raiteri, B. W. Skelton, S. Stagni, M. Massi and
D. H. Brown, Dalton Trans., 2011, 40, 11960.
51 Q.-H. Wei, F.-N. Xiao, L.-J. Han, S.-L. Zeng, Y.-N. Duan and G.-N. Chen,
Dalton Trans., 2011, 40, 5078.
52 R. D. Costa, E. Ort , H. J. Bolink, F. Monti, G. Accorsi and N. Armaroli,
Angew. Chem. Int. Ed., 2012, 51, 81788211.
53 I. S. Shin, H. C. Lim, J. W. Oh, J. K. Lee, T. H. Kim and H. Kim, Electrochem.
Commun., 2011, 13, 6467.
54 W. J. Xu, S. J. Liu, T. C. Ma, Q. Zhao, A. Pertegas, D. Tordera, H. J. Bolink,
S. H. Ye, X. M. Liu, S. Sun and W. Huang, J. Mater. Chem., 2011, 21,
1399914007.
Photochemistry, 2013, 41, 156181 | 175

Downloaded by University of Lancaster on 17/01/2015 22:23:30.

Published on 31 October 2013 on http://pubs.rsc.org | doi:10.1039/9781849737722-00156

View Online

55 H. B. Wu, H. F. Chen, C. T. Liao, H. C. Su and K. T. Wong, Org. Electron.,

2012, 13, 483490.
56 Y. Hisamatsu and S. Aoki, Eur. J. Inorg. Chem., 2011, 5360.
57 M. Li, H. Zeng, Y. Meng, H. Sun, S. Liu, Z. Lu, Y. Huang and X. Pu, Dalton
Trans., 2011, 40, 7153.
58 R. Wang, D. Liu, H. Ren, T. Zhang, X. Wang and J. Li, J. Mater. Chem.,
2011, 21, 15494.
59 E. Barano, S. Fantacci, F. De Angelis, X. Zhang, R. Scopelliti, M. Graetzel
and M. K. Nazeeruddin, Inorg. Chem., 2011, 50, 451.
60 S. Aoki, Y. Matsuo, S. Ogura, H. Ohwada, Y. Hisamatsu, S. Moromizato and
M. Shiro andM. Kitamura, Inorg. Chem., 2011, 50, 806.
61 Y. Koga, M. Kamo, Y. Yamada, T. Matsumoto and K. Matsubara, Eur. J.
Inorg. Chem., 2011, 2869.
62 E. Barano, B. F. E. Curchod, F. Monti, F. Steimer, G. Accorsi, I. Tavernelli,
U. Rothlisberger, R. Scopelliti, M. Gratzel and Md. K. Nazeeruddin, Inorg.
Chem., 2012, 51(2), 799811.
63 C. E. McCusker, D. Hablot, R. Ziessel and F. N. Castellano, Inorg. Chem.,
2012, 51(15), 79577959.
64 K. K.-W. Lo, K. Y. Zhang and S. P.-Y. Li, Pure Appl. Chem., 2011, 83(4),
823840.
65 D. L. Davies, M. P. Lowe, K. S. Ryder, K. Singh and S. Singh, Dalton Trans.,
2011, 40, 1028.
66 S. Ladouceur, D. Fortin and E. Zysman-Colman, Inorg. Chem., 2011, 50,
11514.
67 Y. Wu, H. Jing, Z. Dong, Q. Zhao, H. Wu and F. Li, Inorg. Chem., 2011, 50,
7412.
68 K. R. Schwartz and K. R. Mann, Inorg. Chem., 2011, 50, 12477.
69 F. Spaenig, J.-H. Olivier, V. Prusakova, P. Retailleau, R. Ziessel and
F. N. Castellano, Inorg. Chem., 2011, 50, 10859.
70 E. S. Andreiadis, D. Imbert, J. Pecaut, A. Calborean, I. Cioni, C. Adamo,
R. Demadrille and M. Mazzanti, Inorg. Chem., 2011, 50, 8197.
71 C.-H. Hsieh, F.-I. Wu, C.-H. Fan, M.-J. Huang, K.-Y. Lu, P.-Y. Chou,
Y.-H. O. Yang, S.-H. Wu, I. C. Chen, S.-H. Chou, K.-T. Wong and C.-H.
Cheng, Chem.Eur. J., 2011, 17, 9180.
72 R. D. Costa, F. Monti, G. Accorsi, A. Barbieri, H. J. Bolink, E. Orti and
N. Armaroli, Inorg. Chem., 2011, 50, 7229.
73 C. Li, M. Yu, Y. Sun, Y. Wu, C. Huang and F. Li, J. Am. Chem. Soc., 2011,
133, 11231.
74 J. Sun, W. Wu, H. Guo and J. Zhao, Eur. J. Inorg. Chem., 2011, 3165.
75 C. Wang and K. M.-C. Wong, Inorg. Chem., 2011, 50, 5333.
76 Y.-Y. Chang, J.-Y. Hung, Y. Chi, J.-P. Chyn, M.-W. Chung, C.-L. Lin,
P.-T. Chou, G.-H. Lee, C.-H. Chang and W.-C. Lin, Inorg. Chem., 2011, 50, 5075.
77 D. N. Kozhevnikov, V. N. Kozhevnikov, M. Z. Shakov, A. M. Prokhorov,
D. W. Bruce and J. A. G. Williams, Inorg. Chem., 2011, 50, 3804.
78 E. Barano, E. Orselli, L. Allouche, D. Di Censo, R. Scopelliti, M. Graetzel
and M. K. Nazeeruddin, Chem. Commun., 2011, 47, 2799.
79 G. Nasr, A. Guerlin, F. Dumur, L. Beouch, E. Dumas, G. Clavier,
F. Miomandre, F. Goubard, D. Gigmes, D. Bertin, G. Wantze and C. R.
Mayer, Chem. Commun., 2011, 47, 10698.
80 R. M. Edkins, S. L. Bettington, A. E. Goeta and A. Beeby, Dalton Trans.,
2011, 40, 12765.
81 W. Yang, S. Zhang, Y. Ding, L. Shi and Q. Song, Chem. Commun., 2011, 47,
5310.
176 | Photochemistry, 2013, 41, 156181

Downloaded by University of Lancaster on 17/01/2015 22:23:30.

Published on 31 October 2013 on http://pubs.rsc.org | doi:10.1039/9781849737722-00156

View Online

82 T. Lazarides, T. M. McCormick, K. C. Wilson, S. Lee, D. W. McCamant and

R. Eisenberg, J. Am. Chem. Soc., 2011, 133, 350.
83 M. T. Whited, P. I. Djurovich, S. T. Roberts, A. C. Durrell, C. W. Schlenker,
S. E. Bradforth and M. E. Thompson, J. Am. Chem. Soc., 2011, 133, 88.
84 E. Rossi, L. Murphy, P. L. Brothwood, A. Colombo, C. Dragonetti,
D. Roberto, R. Ugo, M. Cocchi and J. A. G. Williams, J. Mater. Chem., 2011,
21, 15501.
85 V. Prusakova, C. E. McCusker and Felix N. Castellano, Inorg. Chem., 2012,
51(15), 85898598.
86 W. Wu, W. Wu, S. Ji, H. Guo and J. Zhao, Dalton Trans., 2011, 40, 5953.
87 A. Y.-Y. Tam, D. P.-K. Tsang, M.-Y. Chan, N. Zhu and V. W.-W. Yam,
Chem. Commun., 2011, 47, 3383.
88 S. C. F. Kui, Y.-C. Law, G. S. M. Tong, W. Lu, M.-Y. Yuen and C.-M. Che,
Chem. Sci., 2011, 2, 221.
89 Z. M. Hudson, M. G. Helander, Z.-H. Lu and S. Wang, Chem. Commun.,
2011, 47, 755.
90 G. Xu, Q. Luo, S. Eibauer, A. F. Rausch, S. Stempfhuber, M. Zabel, H. Yersin
and O. Reiser, Dalton Trans., 2011, 40, 8800.
91 S. Jamali, R. Czerwieniec, R. Kia, Z. Jamshidi and M. Zabel, Dalton Trans.,
2011, 40, 9123.
92 H.-M. Wen, Y.-H. Wu, L.-J. Xu, L.-Y. Zhang, C.-N. Chen and Z.-N. Chen,
Dalton Trans., 2011, 40, 6929.
93 H. E. Abdou, A. A. Mohamed, J. M. Lopez-de-Luzuriaga, M. Monge and
J. P. Fackler Jr., In org. Chem., 2012, 51(4), 20102015.
94 N. Minh-Hai and J. H. K. Yip, Organometallics, 2011, 30, 6383.
95 W. Wu, H. Guo, W. Wu, S. Ji and J. Zhao, Inorg. Chem., 2011, 50, 11446.
96 D. A. K. Vezzu, D. Ravindranathan, A. W. Gamer, L. Bartolotti,
M. E. Smith, P. D. Boyle and S. Huo, Inorg. Chem., 2011, 50, 8261.
97 M. N. Roberts, J. K. Nagle, M. B. Majewski, J. G. Finden, N. R. Branda and
M. O. Wolf, Inorg. Chem., 2011, 50, 4956.
98 Y. Zhang, J. A. Garg, C. Michelin, T. Fox, O. Blacque and K. Venkatesan,
Inorg. Chem., 2011, 50, 1220.
99 Z. Ji, Y. Li, T. M. Pritchett, N. S. Makarov, J. E. Haley, Z. Li, M. Drobizhev,
A. Rebane and W. Sun, Chem.Eur. J., 2011, 17, 2479.
100 J. Ding, K. Feng, C.-H. Tung and L.-Z. Wu, J. Phys. Chem. C, 2011, 115, 833.
101 J. E. Haley, D. M. Krein, J. L. Monahan, A. R. Burke, D. G. McLean,
J. E. Slagle, A. Fratini and T. M. Cooper, J. Phys. Chem. A, 2011, 115, 265.
102 L. Rodr guez, M. Ferrer, R. Crehuet, J. Anglada and J. C. Lima, Inorg. Chem.,
2012, 51(14), 76367641.
103 V. K.-M. Au, W. H. Lam, W.-T. Wong and V. W.-W. Yam, Inorg. Chem.,
2012, 51(14), 75377545.
104 J.-H. Jia, J.-X. Liang, Z. Lei, Z.-X. Cao and Q.-M. Wang, Chem. Commun.,
2011, 47, 4739.
105 E. Rabinovich, I. Goldberg and Z. Gross, Chem.Eur. J., 2011, 17, 12294.
106 I. O. Koshevoy, C.-L. Lin, A. J. Karttunen, J. Jaenis, M. Haukka, S. P. Tunik,
P.-T. Chou and T. A. Pakkanen, Chem.Eur. J., 2011, 17, 11456.
107 W. Lu, W.-M. Kwok, C. Ma, C. T.-L. Chan, M.-X. Zhu and C.-M. Che,
J. Am. Chem. Soc., 2011, 133, 14120.
108 J. M. Lopez-de-Luzuriaga, M. Monge, M. E. Olmos, D. Pascual and
M. Rodriguez- Castillo, Inorg. Chem., 2011, 50, 6910.
109 J. A. Garg, O. Blacque and K. Venkatesan, Inorg. Chem., 2011, 50, 5430.
110 V. K.-M. Au, K. M.-C. Wong, N. Zhu and V. W.-W. Yam, Chem.Eur. J.,
2011, 17, 130.
Photochemistry, 2013, 41, 156181 | 177

Downloaded by University of Lancaster on 17/01/2015 22:23:30.

Published on 31 October 2013 on http://pubs.rsc.org | doi:10.1039/9781849737722-00156

View Online

111 M. Arca, T. Aroz, M. Concepcion Gimeno, M. Kulcsar, A. Laguna,

T. Lasanta, V. Lippolis, J. M. Lopez-de-Luzuriaga, M. Monge and M. Elena
Olmos, Eur. J. Inorg. Chem., 2011, 2288.
112 E. J. Fernandez, A. Laguna, J. M. Lopez-de-Luzuriaga, M. Monge and
E. Sanchez- Forcada, Dalton Trans., 2011, 40, 3287.
113 J. Wang, W. Lin, L. Yuan, J. Song and W. Gao, Chem. Commun., 2011, 47,
12506.
114 G. F. Manbeck, W. W. Brennessel and R. Eisenberg, Inorg. Chem., 2011, 50,
3431.
115 Y. You, Y. Han, Y.-M. Lee, S. Y. Park, W. Nam and S. J. Lippard, J. Am.
Chem. Soc., 2011, 133, 11488.
116 B. Bozic-Weber, E. C. Constable, C. E. Housecroft, P. Kopecky,
M. Neuburger and J. A. Zampese, Dalton Trans., 2011, 40, 12584.
117 J. Min, Q. Zhang, W. Sun, Y. Cheng and L. Wang, Dalton Trans., 2011, 40,
686.
118 R. D. Costa, D. Tordera, E. Orti, H. J. Bolink, J. Schoenle, S. Graber,
C. E. Housecroft, E. C. Constable and J. A. Zampese, J. Mater. Chem., 2011,
21, 16108.
119 C. S. Lim, J. H. Han, C. W. Kim, M. Y. Kang, D. W. Kang and B. R. Cho,
Chem. Commun., 2011, 47, 7146.
120 B. Mondal, P. Kumar, P. Ghosh and A. Kalita, Chem. Commun., 2011, 47,
2964.
121 P. Li, X. Duan, Z. Chen, Y. Liu, T. Xie, L. Fang, X. Li, M. Yin and B. Tang,
Chem. Commun., 2011, 47, 7755.
122 C. S. Smith and K. R. Mann, J. Am. Chem. Soc., 2012, 134(21), 87868789.
123 J. Huang, O. Buyukcakir, M. W. Mara, A. Coskun, N. M. Dimitrijevic,
G. Barin, O. Kokhan, A. B. Stickrath, R. Ruppert, D. M. Tiede, J. F. Stoddart,
J. P. Sauvage and L. X. Chen, Angew. Chem. Int. Ed., 2012, 51, 1271112715.
124 J. Vuojola, I. Hyppanen, M. Nummela, J. Kankare and T. Soukka, J. Phys.
Chem. B, 2011, 115, 13685.
125 E. Di Piazza, L. Norel, K. Costuas, A. Bourdolle, O. Maury and S. Rigaut,
J. Am. Chem. Soc., 2011, 133, 6174.
126 W. Jiang, B. Lou, J. Wang, H. Lv, Z. Bian and C. Huang, Dalton Trans., 2011,
40, 11410.
127 P. Lian, H. Wei, C. Zheng, Y. Nie, J. Bian, Z. Bian and C. Huang, Dalton
Trans., 2011, 40, 5476.
128 T. D. Pasatoiu, C. Tiseanu, A. M. Madalan, B. Jurca, C. Duhayon, J. P. Sutter
and M. Andruh, Inorg. Chem., 2011, 50, 5879.
129 D. Sykes, I. S. Tidmarsh, A. Barbieri, I. V. Sazanovich, J. A. Weinstein and
M. D. Ward, Inorg. Chem., 2011, 50, 11323.
130 D. Sykes and M. D. Ward, Chem. Commun., 2011, 47, 2279.
131 J. Xu, T. M. Corneillie, E. G. Moore, G.-L. Law, N. G. Butlin and
K. N. Raymond, J. Am. Chem. Soc., 2011, 133, 19900.
132 T. Zhang, X. Zhu, C. C. W. Cheng, W.-M. Kwok, H.-L. Tam, J. Hao,
D. W. J. Kwong, W.-K. Wong and K.-L. Wong, J. Am. Chem. Soc., 2011, 133,
20120.
133 J. Andres and A.-S. Chauvin, Inorg. Chem., 2011, 50, 10082.
134 M. Tropiano, N. L. Kilah, M. Morten, H. Rahman, J. J. Davis, P. D. Beer and
S. Faulkner, J. Am. Chem. Soc., 2011, 133, 11847.
135 A. Brandner, T. Kitahara, N. Beare, C. Lin, M. T. Berry and P. S. May, Inorg.
Chem., 2011, 50, 6509.
136 J. Yuasa, T. Ohno, K. Miyata, H. Tsumatori, Y. Hasegawa and T. Kawai,
J. Am. Chem. Soc., 2011, 133, 9892.
178 | Photochemistry, 2013, 41, 156181

Downloaded by University of Lancaster on 17/01/2015 22:23:30.

Published on 31 October 2013 on http://pubs.rsc.org | doi:10.1039/9781849737722-00156

View Online

137 Y. O. Fung, W. Wu, C.-T. Yeung, H.-K. Kong, K. K.-C. Wong, W.-S. Lo,
G.-L. Law, K.-L. Wong, C.-K. Lau, C.-S. Lee and W.-T. Wong, Inorg. Chem.,
2011, 50, 5517.
138 M. P. Placidi, J. Engelmann, L. S. Natrajan, N. K. Logothetis and
G. Angelovski, Chem. Commun., 2011, 47, 11534.
139 M. Andrews, J. E. Jones, L. P. Harding and S. J. A. Pope, Chem. Commun.,
2011, 47, 206.
140 V. Aubert, L. Ordronneau, M. Escadeillas, J. A. G. Williams, A. Boucekkine,
E. Coulaud, C. Dragonetti, S. Righetto, D. Roberto, R. Ugo, A. Valore,
A. Singh, J. Zyss, I. Ledoux-Rak, H. Le Bozec and V. Guerchais, Inorg.
Chem., 2011, 50, 5027.
141 V. Divya, R. O. Freire and M. L. P. Reddy, Dalton Trans., 2011, 40, 3257;
N. N. Katia, A. Lecointre, M. Regueiro-Figueroa, C. Platas-Iglesias and L. J.
Charbonniere, Inorg. Chem., 2011, 50, 1689.
142 D. J. Lewis, P. B. Glover, M. C. Solomons and Z. Pikramenou, J. Am. Chem.
Soc., 2011, 133, 1033.
143 Y. Zhong, L. Si, H. He and A. G. Sykes, Dalton Trans., 2011, 40, 11389.
144 M. M. Nolasco, P. D. Vaz and L. D. Carlos, New J. Chem., 2011, 35, 2435.
145 S. Mizukami, T. Yamamoto, A. Yoshimura, S. Watanabe and K. Kikuchi,
Angew. Chem., Int. Ed., 2011, 50, 8750.
146 Y. Chen, W. Guo, Z. Ye, G. Wang and J. Yuan, Chem. Commun., 2011, 47, 6266.
147 N. Alzakhem, C. Bischof and Michael Seitz, Inorg. Chem., 2012, 51(17),
93439349.
148 C. Doek, N. Alzakhem, C. Bischof, J. Wahsner, T. Guden-Silber, J. Lugger,
C. Platas-Iglesias and Michael Seitz, J. Am. Chem. Soc., 2012, 134(39),
1641316423.
149 G.-L. Law, T. A. Pham, J. Xu and K. N. Raymond, Angew. Chem. Int. Ed.,
2012, 51, 23712374.
150 C.-L. Pan, Y.-S. Pan, J. Wang and J.-F. Song, Dalton Trans., 2011, 40, 6361.
151 H.-B. Xu, J. Li, L.-X. Shi and Z.-N. Chen, Dalton Trans., 2011, 40, 5549.
152 C. Kachi-Terajima, K. Yanagi, T. Kaziki, T. Kitazawa and M. Hasegawa,
Dalton Trans., 2011, 40, 2249.
153 J. Jankolovits, C. M. Andolina, J. W. Kampf, K. N. Raymond and
V. L. Pecoraro, Angew. Chem., Int. Ed., 2011, 50, 9660.
154 O. Kotova, S. Comby and T. Gunnlaugsson, Chem. Commun., 2011, 47, 6810.
155 M. P. Redmond, S. M. Cornet, S. D. Woodall, D. Whittaker, D. Collison,
M. Helliwell and L. S. Natrajan, Dalton Trans., 2011, 40, 3914.
156 K. Miyata, T. Nakagawa, R. Kawakami, Y. Kita, K. Sugimoto, T.
Nakashima, T. Harada, T. Kawai and Y. Hasegawa, Chem.-Eur. J., 2011, 17, 521.
157 Y. Lu, S. Huang, Y. Liu, S. He, L. Zhao and X. Zeng, Org. Lett., 2011, 13,
5274.
158 J. Vestfrid, M. Botoshansky, J. H. Palmer, A. C. Durrell, H. B. Gray and
Z. Gross, J. Am. Chem. Soc., 2011, 133, 12899.
159 C. Perez-Bolivar, S.-Y. Takizawa, G. Nishimura, V. A. Montes and
P. Anzenbacher, Chem. Eur. J., 2011, 17, 9076.
160 J. P. Heiskanen, A. E. Tolkki, H. J. Lemmetyinen and O. E. O. Hormi,
J. Mater. Chem., 2011, 21, 14766.
161 M. Krayer, E. Yang, H.-J. Kim, H. L. Kee, R. M. Deans, C. E. Sluder,
J. R. Diers, C. Kirmaier, D. F. Bocian, D. Holten and J. S. Lindsey, Inorg.
Chem., 2011, 50, 4607.
162 R. L. Arrowsmith, P. A. Waghorn, M. W. Jones, A. Bauman, S. K. Brayshaw,
Z. Hu, G. Kociok-Koehn, T. L. Mindt, R. M. Tyrrell, S. W. Botchway, J. R.
Dilworth and S. I. Pascu, Dalton Trans., 2011, 40, 6238.
Photochemistry, 2013, 41, 156181 | 179

Downloaded by University of Lancaster on 17/01/2015 22:23:30.

Published on 31 October 2013 on http://pubs.rsc.org | doi:10.1039/9781849737722-00156

View Online

163 S. M. Crawford, A. A.-S. Ali, T. S. Cameron and A. Thompson, Inorg. Chem.,

2011, 50, 8207.
164 R. Czerwieniec, J. Yu and H. Yersin, Inorg. Chem., 2011, 50, 8293.
165 C. Sun, P. U. Thakker, L. Khulordava, D. J. Tobben, S. M. Greenstein,
D. L. Grisenti, A. G. Kantor and P. S. Wagenknecht, Inorg. Chem., 2012,
51(20), 1047710479.
166 J. D. Chartres, M. Busby, M. J. Riley, J. J. Davis and P. V. Bernhardt, Inorg.
Chem., 2011, 50, 9178.
167 P. Li, L. Fang, H. Zhou, W. Zhang, X. Wang, N. Li, H. Zhong and B. Tang,
Chem.-Eur. J., 2011, 17, 10519.
168 M. N. Sokolov, M. A. Mihailov, E. V. Peresypkina, K. A. Brylev,
N. Kitamura and V. P. Fedin, Dalton Trans., 2011, 40, 6375.
169 J. Schneider, K. Q. Vuong, J. A. Calladine, X.-Z. Sun, A. C. Whitwood,
M. W. George and R. N. Perutz, Inorg. Chem., 2011, 50, 11877.
170 J. D. Knoll, S. M. Arachchige, G. Wang, K. Rangan, R. Miao,
S. L. H. Higgins, B. Okyere, M. Zhao, P. Croasdale, K. Magruder, B. Sinclair,
C. Wall and K. J. Brewer, Inorg. Chem., 2011, 50, 8850.
171 R. Siebert, C. Hunger, J. Guthmuller, F. Schluetter, A. Winter, U. S. Schubert,
L. Gonzalez, B. Dietzek and J. Popp, J. Phys. Chem. C, 2011, 115, 12677.
172 S.-H. Wu, S. E. Burkhardt, J. Yao, Y.-W. Zhong and H. D. Abruna, Inorg.
Chem., 2011, 50, 3959.
173 D. Saha, S. Das, D. Maity, S. Dutta and S. Baitalik, Inorg. Chem., 2011, 50, 46.
174 V. N. Kozhevnikov, M. C. Durrant and J. A. G. Williams, Inorg. Chem., 2011,
50, 6304.
175 C. K. M. Chan, C.-H. Tao, K.-F. Li, K. M.-C. Wong, N. Zhu, K.-W. Cheah
and V. W.-W. Yam, Dalton Trans., 2011, 40, 10670.
176 L. Aboshyan-Sorgho, C. Besnard, P. Pattison, K. R. Kittilstved, A. Aebischer,
J.-C. G. Buenzli, A. Hauser and C. Piguet, Angew. Chem., Int. Ed., 2011, 50,
4108.
177 B. Ventura, A. Barbieri, A. Degli Esposti, J. Batcha Seneclauze and R. Ziessel,
Inorg. Chem., 2012, 51, 28322840.
178 A. Damas, B. Ventura, J. Moussa, A. Degli Esposti, L.-M. Chamoreau,
A. Barbieri and H. Amouri, Inorg. Chem., 2012, 51(3), 17391750.
179 J. K. Sprafke, D. V. Kondratuk, M. Wykes, A. L. Thompson, M. Homann,
R. Drevinskas, W.-H. Chen, C. K. Yong, J. Karnbratt, J. E. Bullock,
M. Malfois, M. R. Wasielewski, B. Albinsson, L. M. Herz, D. Zigmantas,
D. Beljonne and H. L. Anderson, J. Am. Chem. Soc., 2011, 133, 17262.
180 A. Yella, H.-W. Lee, H. N. Tsao, C. Yi, A. K. Chandiran, M. K. Nazeeruddin,
E. W.-G. Diau, C.-Y. Yeh, S. M. Zakeeruddin and M. Graetzel, Science, 2011,
334, 629.
181 F. Bregier, S. M. Aly, C. P. Gros, J.-M. Barbe, Y. Rousselin and P. D. Harvey,
Chem. Eur. J., 2011, 17, 14643.
182 L. P. Hernandez-Eguia, E. C. Escudero-Adan, I. C. Pintre, B. Ventura,
L. Flamigni and P. Ballester, Chem. Eur. J., 2011, 17, 14564.
183 S. K. Sugunan, B. Robotham, R. P. Sloan, J. Szmytkowski, K. P. Ghiggino,
M. F. Paige and R. P. Steer, J. Phys. Chem. A, 2011, 115, 12217.
184 A. Chaudhary and S. P. Rath, Chem. Eur. J., 2011, 17, 11478.
185 F. Javier Cespedes-Guirao, K. Ohkubo, S. Fukuzumi, F. Fernandez-Lazaro
and A. Sastre-Santos, Chem.Asian J., 2011, 6, 3110.
186 A. Ray, K. Santhosh and S. Bhattacharya, J. Phys. Chem. A, 2011, 115, 9929.
187 A. M. V. M. Pereira, A. R. M. Soares, A. Hausmann, M. G. P. M. S. Neves,
A. C. Tome, A. M. S. Silva, J. A. S. Cavaleiro, D. M. Guldi and T. Torres,
Phys. Chem. Chem. Phys., 2011, 13, 11858.
180 | Photochemistry, 2013, 41, 156181

Downloaded by University of Lancaster on 17/01/2015 22:23:30.

Published on 31 October 2013 on http://pubs.rsc.org | doi:10.1039/9781849737722-00156

View Online

188 J. Iehl, M. Vartanian, M. Holler, J.-F. Nierengarten, B. Delavaux-Nicot,

J.-M. Strub, A. Van Dorsselaer, Y. Wu, J. Mohanraj, K. Yoosaf and
N. Armaroli, J. Mater. Chem., 2011, 21, 1562.
189 F. DSouza, C. A. Wijesinghe, M. E. El-Khouly, J. Hudson, M. Niemi,
H. Lemmetyinen, N. V. Tkachenko, M. E. Zandler and S. Fukuzumi, Phys.
Chem. Chem. Phys., 2011, 13, 18168.
190 A. J. Jimenez, B. Grimm, V. L. Gunderson, M. T. Vagnini, S. K. Calderon,
M. SalomeRodriguez-Morgade, M. R. Wasielewski, D. M. Guldi and
T. Torres, Chem.Eur. J., 2011, 17, 5024.
191 R. R. Dasari, M. M. Sartin, M. Cozzuol, S. Barlow, J. W. Perry and
S. R. Marder, Chem. Commun., 2011, 47, 4547.
192 V. S. Shetti and M. Ravikanth, Inorg. Chem., 2011, 50, 1713.
193 A. V. Soldatova, J. Kim, C. Rizzoli, M. E. Kenney, M. A. J. Rodgers, A. Rosa
and G. Ricciardi, Inorg. Chem., 2011, 50, 1135.
194 P. DAmbrosio, L. Tonucci, N. dAlessandro, A. Morvillo, S. Sortino and
M. Bressan, Eur. J. Inorg. Chem., 2011, 503.
195 L. Le Pleux, Y. Pellegrin, E. Blart, F. Odobel and A. Harriman, J. Phys. Chem.
A, 2011, 115, 5069.
196 Y. Li, Y. Bian, M. Yan, P. S. Thapaliya, D. Johns, X. Yan, D. Galipeau and
J. Jiang, J. Mater. Chem., 2011, 21, 11131.

Photochemistry, 2013, 41, 156181 | 181