ARTICLE

[Link]/IC

Phosphorescence vs Fluorescence in Cyclometalated Platinum(II) and

Iridium(III) Complexes of (Oligo)thienylpyridines
Dmitry N. Kozhevnikov,*,†,‡ Valery N. Kozhevnikov,§ Marsel Z. Shafikov,‡ Anton M. Prokhorov,‡,||
Duncan W. Bruce,*,|| and J. A. Gareth Williams*,^
†
I. Postovsky Institute of Organic Synthesis, Ekaterinburg, 620041, Russia
‡
Ural Federal University, Mira 19, Ekaterinburg, 620002, Russia
§
School of Life Sciences, Northumbria University, Newcastle-Upon-Tyne, Ne1 8st, United Kingdom
)

Department of Chemistry, University of York, Heslington, York, Yo10 5dd, United Kingdom
^
Department of Chemistry, Durham University, South Road, Durham, Dh1 3le, United Kingdom

bS Supporting Information
Downloaded by INST OF CHEMISTRY at [Link] on June 14, 2019

ABSTRACT: Two newly prepared oligothienylpyridines, 5-(2-

pyridyl)-50 -dodecyl-2,20 -bithiophene, HL2, and 5-(2-pyridyl)-500 -
dodecyl-2,20 :50 ,200 -ter-thiophene, HL3, bind to platinum(II) and
iridium(III) as N∧C-coordinating ligands, cyclometallating at
from [Link]

position C4 in the thiophene ring adjacent to the pyridine, leaving

a chain of either one or two pendent thiophenes. The synthesis of
complexes of the form [PtLn(acac)] and [Ir(Ln)2(acac)] (n = 2
or 3) is described. The absorption and luminescence properties of
these four new complexes are compared with the behavior of the
known complexes [PtL1(acac)] and [Ir(L1)2(acac)] {HL1 =
2-(2-thienyl)pyridine}, and the profound differences in behav-
ior are interpreted with the aid of time-dependent density
functional theory (TD-DFT) calculations. Whereas [PtL1(acac)] displays solely intense phosphorescence from a triplet state
of mixed ππ*/MLCT character, the phosphorescence of [PtL2(acac)] and [PtL3(acac)] is weak, strongly red shifted, and
accompanied by higher-energy fluorescence. TD-DFT reveals that this difference is probably due to the metal character in the
lowest-energy excited states being strongly attenuated upon introduction of the additional thienyl rings, such that the
spin
orbit coupling effect of the metal in promoting intersystem crossing is reduced. A similar pattern of behavior is observed
for the iridium complexes, except that the changeover to dual emission is delayed to the terthiophene complex [Ir(L3)2(acac)],
reflecting the higher degree of metal character in the frontier orbitals of the iridium complexes than their platinum
counterparts.

’ INTRODUCTION fluorescence is not commonly observed from discrete complexes

Complexes of iridium(III) and platinum(II) with heterocyclic of the third-row transition-metal complexes, although a few
ligands, such as polypyridines and their cyclometallating aryl examples are known, for example, where a ligand incorporates
analogues, have found a wide range of applications in the context a π-conjugated chromophoric ligand somewhat remote from the
of photoactive molecular materials.1,2 These include metal center.9
photocatalysts,3 photochemical solar energy conversion,4 biolo- In order for the metal ion to exert the above SOC effects and
gical labels,5 and, in particular, phosphorescent dopants in the promote phosphorescence, its orbitals should make a significant
electroluminescent layers of organic light-emitting diodes contribution to the frontier orbitals involved in the excited states.
(OLEDs).6 The high spin
orbit coupling (SOC) associated For larger complexes with more extended ligands or in which
with the heavy metal atom can promote the triplet f singlet there is a saturated linker between the metal-containing moiety
radiative transition, so that such complexes may exhibit unusually and that part of the molecule on which the excited state is
high phosphorescence quantum yields at room temperature and primarily localized, the influence of the metal is expected to be
relatively short triplet emission decay times.7 In addition, inter- attenuated. Typically, this may lead to longer triplet radiative
system crossing (ISC) from the singlet (S1) to the triplet state lifetimes, as the excited state becomes more like a purely organic
(typically T1) is also accelerated and normally depopulates the
former at a rate (1012 s
1) much faster than that of radiative Received: January 31, 2011
emission from the singlet state (108
109 s
1).8 As a result, Published: March 23, 2011

r 2011 American Chemical Society 3804 [Link]/10.1021/ic200210e | Inorg. Chem. 2011, 50, 3804–3815
Inorganic Chemistry ARTICLE

one, although the rate of S f T ISC may still be sufficient to decay pathways unexpectedly limit efficiencies severely com-
eliminate fluorescence. Elongation of the luminescence lifetimes pared both to the fluorescence of oligothiophenes and to the
of iridium terpyridyl complexes upon going from phenyl to phosphorescence of the parent, unsubstituted cyclometalated
biphenyl substituents is an example of such a case.10 Meanwhile, complexes. The results are interpreted with the aid of calculations
Chi and Chou and co-workers made a detailed study of dual using time-dependent density functional theory (TD-DFT).
emission in a series of osmium complexes, in which the propor-
tion of fluorescence to phosphorescence varied according to the ’ RESULTS AND DISCUSSION
identity of a π-conjugated aromatic system appended to a
β-diketonate ligand.11 Key points relating to the attenuation of 1. Synthesis of Ligands and Complexes. New proligands—
SOC in such complexes have been reviewed recently.11b There pyridines with bi- or terthiophene chains at position 2—were
are also some cases of Pt(II) complexes, particularly those in synthesized by the Stille couplings of appropriate bromothienylpyr-
which the ligands have been appended with additional moieties idines and 2-(tributyltin)thiophene. A dodecyl chain was incorpo-
favoring, for example, charge-transport properties for use in rated into the ligands in order to increase their solubility and,
OLEDs, which show dual luminescence (typically dominant especially, the solubility of the ensuing complexes. The reaction
fluorescence from a remote organic substituent and minor of 2-(2-bromothien-5-yl)pyridine, 1, with 2-(tributyltin)-5-dodecyl-
phosphorescence related with the metal and ligating unit).12 thiophene, 2, in the presence of tetrakis-(triphenylphosphine)
Cyclometalated iridium(III) and platinum(II) complexes of palladium(0) as catalyst gave proligand HL2 bearing a bithiophene
arylpyridines are well known to be often strongly phosphores- moiety (Scheme 1). The same reaction of 1 with 2-(tributyltin)
cent at room temperature.13
15 Chemical modification of the thiophene, 3, followed by bromination of the resulting bithie-
chromophoric cyclometallating ligand enables tuning of the nylpyridine, 4, gave the halogen precursor 5. Finally, the cross-
emitting properties in a manner that can be readily understood coupling reaction of 5 with 2 gave the terthienylpyridine
in terms of the influence of electron-donating and -withdrawing proligand HL3.
substituents on the energies of the frontier orbitals.16 Iridium Platinum complexes incorporating the new ligands L2 and L3
complexes of such ligands, in particular, have attracted a great coordinated to the metal in a cyclometalated N∧C30 fashion,
deal of interest as OLED phophors, for example, [Ir(ppy)3], [PtLn(acac)], were obtained through the intermediacy of the
[Ir(F2ppy)2(pic)], and [Ir(piq)2(acac)] as green, blue, and red dichloro-bridged dimer complexes [PtLn(μ-Cl)]2 and their
emitters, respectively {ppyH = 2-phenylpyridine; F2ppyH = reaction with sodium acetylacetonate in acetone in a modifica-
2-(2,4-difluorophenyl)pyridine; piqH = 1-phenylisoquinoline; tion to the previously described procedure for [Pt(ppy)(acac)]14
picH = picolinic acid; acacH = 2,4-pentanedione}.17
19 Thie- (Scheme 2). The corresponding cyclometalated iridium com-
nylpyridines, in which the phenyl group has been replaced by a plexes [Ir(Ln)2(acac)] were obtained in a one-pot procedure
thiophene ring, are also potentially interesting ligands for gen- upon reaction of the proligands HL2 and HL3 with IrCl3 3 xH2O
erating luminescent complexes. The more electron-rich nature of and sodium acetylacetonate in ethoxyethanol under reflux
the thiophene ring compared to the benzene ring is known to (Scheme 2). In the sections which follow, the platinum(II) and
lead to red shifts in the emission energy of thienylpyridine iridium(III) complexes of L1, L2, and L3 will be abbreviated Pt-1,
complexes compared to those of ppy, an effect attributed Pt-2, and Pt-3 and Ir-1, Ir-2, and Ir-3, respectively (Figure 1).
primarily to destabilization of the highest occupied orbitals 2. UV
Visible Absorption and Emission Spectroscopy of
{thpy =2-(2-thienyl)pyridine}. the Proligands HL1
HL3. The absorption spectra of the
Meanwhile, oligo- and polythiophenes, long a source of proligands are shown in Figure 2, and numerical absorption
fascination for the conducting properties that arise upon doping and emission data for all compounds are summarized in Table 1.
them with electrons or holes,20 are also of interest for their The extension from one to two to three thiophenes leads to a
fluorescence properties. Typically, they have high quantum yields progressive shift in the lowest-energy absorption band to longer
of fluorescence, with emission energies that are influenced wavelengths, as typically observed for polyaryls. Introduction of
sensitively by molecular and environmental factors, properties the second thiophene unit stabilizes the excited state by
that have been exploited in fluorescent sensory systems, among 5500 cm
1, while the third leads to a smaller decrease of
others.21 2500 cm
1. This red shift is accompanied by a substantial
The combination of these two types of molecular units, increase in the extinction coefficient.
namely, an oligothiophene and a cyclometalated thienylpyridine, All three compounds are fluorescent in solution at room
should thus be an intriguing system to consider and is the subject temperature (Figure 3 and Table 1). The emission band shows
of the current paper. We describe the synthesis and photophy- a shift to longer wavelength upon elongaton of the thiophene
sical properties of cyclometalated Pt(II) and Ir(III) complexes of chain, which is quantitatively similar to that observed in absorp-
2-(oligothienyl)pyridines. The molecules are derivatives of the tion. A hint of vibrational structure can be discerned for HL2 and
known compounds [PtL1(acac)] and [Ir(L1)2(acac)], where HL3, which becomes fully resolved in the spectra recorded at 77
HL1 = 2-(2-thienyl)pyridine (here studied as models), carrying K (∼1400 cm
1). The emission lifetimes are <1 ns at 298 K and
either one or two additional thiophene rings on the metalated around 2 ns at 77 K. Notably, no phosphorescence was observed
thienyl ring. One might reason that the metal ion would promote even at 77 K, suggesting that the rate of intersystem crossing to
formation of the triplet state of the oligothiophene, leading to the triplet state is much slower than the radiative rate of
efficient low-energy phosphorescence, or that the extended fluorescence.
nature of the ligand might attentuate the effect of the metal, 3. UV
Visible Absorption and Emission Spectroscopy of
such that formation of the triplet state would become inefficient the Pt(II) Complexes Pt-1, Pt-2, and Pt-3. The absorption
and fluorescence might compete effectively. We show that the spectra of the three platinum complexes are shown in Figure 4.
extension of the ligand does dramatically alter the emission Each complex shows two main sets of bands. The higher energy
properties, fluorescence is indeed observed, but nonradiative bands (at around 300, 350, and 375 nm for Pt-1, Pt-2, and Pt-3,
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Inorganic Chemistry ARTICLE

Scheme 1. Synthesis of the New Proligands HL2 and HL3

Scheme 2. Synthetic Route to the Pt(II) and Ir(III) MeTHF. 14 Our recorded luminescence quantum yield of
Complexes 0.36 ( 0.1 in CH2Cl2 is also substantially higher than the previous
report of 0.11 in MeTHF. Though a solvent effect might be
suspected, we obtained a similar lifetime of 23 μs in MeTHF,
from which we can only conclude that the previously reported
values may have been underestimated. We also note a discre-
pancy between the emission maxima (556 nm in our case in
MeTHF, compared to 575 nm in the earlier report in the same
solvent). On the other hand, our recorded data are in good
agreement with a recent study which included the luminescence
maximum, lifetime, and quantum yield (558 nm, 21 μs, and
0.42, respectively) of Pt-1 in CH2Cl2.22 The highly structured
emission spectrum, whose energy is scarcely affected upon
respectively) appear at roughly comparable positions to those of cooling to 77 K (Table 1), and the relatively long luminescence
the ligands, suggesting that they arise from ligand-based transi- lifetime are suggestive of an emissive state with substantial
tions. Each complex also exhibits a lower-energy band at ligand-centered (LC) character, albeit with sufficient metal
substantially longer wavelength than the absorption of the character to promote the phosphorescence process through
ligands, which are likely to arise from charge-transfer transitions the SOC influence of the metal as well as facilitate the S f T
involving the metal. The origin of these bands is considered ISC and thus eliminate observable ligand-based fluorescence
in more detail with the aid of TD-DFT calculations in the from the singlet state.
subsequent sections. It may be noted here that there is again a The emission spectrum of Pt-2 is very different from that of
trend to longer wavelengths upon elongation of the thiophene Pt-1 in that it displays two sets of bands: a broad, unstructured
chain, as observed in the proligands, with the bands appearing band around 500 nm and bands >700 nm showing some
at around 400, 440, and 460 nm for Pt-1, Pt-2, and Pt-3 evidence of vibrational structure (Figure 5). The intensity of
respectively. both bands is very weak: the total emission quantum yield is
Pt-1 displays strong phosphorescence in deaerated solution at around 2 orders of magnitude lower than that of Pt-1. The
room temperature, as reported previously by Thompson and co- excitation spectra of both the high- and low-energy bands match
workers.14 The emission spectrum is vibrationally well resolved, closely the absorption spectrum of the complex. This observation
with the 0,0 band at 554 nm (Figure 5 and Table 1). No tends to rule out the possibility that the low-energy band might
fluorescence is detectable at higher energies. Two independent arise from a dimer or aggregate species, since such emission is
measurements were made of the phosphorescence lifetime in typically accompanied by an additional band in the excitation/
CH2Cl2 using different instrumentation, one using TCSPC upon absorption spectra, as in the case of MMLCT states, for example.
excitation with a picosecond laser diode source at 374 nm and the Moreover, the relative ratio of the band intensities is independent
other by multichannel scaling with excitation at 420 nm using a of concentration in the range investigated (up to 10
4 M), ruling
xenon microsecond flashlamp. The techniques gave consistent out assignment of the low-energy emission to an excimer. The
results, but the lifetime of 21 ( 2 μs recorded is surprisingly lifetime of the higher-energy emission is <0.5 ns, suggesting that
longer than the value of 4.5 μs previously reported in this band is due to spin-allowed fluorescence from the singlet
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Inorganic Chemistry ARTICLE

Figure 1. Pt(II) and Ir(III) complexes.

once formed, emits with much lower efficiency than Pt-1, leading
to an inferior quantum yield. Both observations would be
consistent with a smaller contribution of metal character (and
hence SOC) in the pertinent excited states, and we return to this
point in section 7. A decrease in ISC with increasing distance of
the baricenter of the conjugated system from the metal has
been similarly demonstrated in a series of osmium(II) com-
plexes bearing aryl acetonate ligands11 and in a pair of Pt(II)
complexes with acetylide substituted hexa-peri-hexbenzocor-
one ligands.9c
Similar dual emission is observed for Pt-3 (Figure 5 and
Table 1). The bands are red shifted compared to those of Pt-2,
which reflects the trend observed in the proligands HL2 and HL3
and attributable to the more extended π-conjugated structure,
although the shift of about 30 nm for both the higher- and lower-
energy bands in the complexes is smaller than that observed in
the proligands. The intensity of the emission is even weaker than
for Pt-2.
4. UV
Visible Absorption and Emission Spectroscopy of
Figure 2. Absorption spectra of HL1, HL2, and HL3 in CH2Cl2 at 298 the Ir(III) Complexes Ir-1, Ir-2, and Ir-3. The photophysical
( 3 K. behavior of the iridium complexes is, to a considerable extent,
quite comparable to that of the platinum analogues. The
state. It is red shifted by around 60 nm compared to the absorption spectra again comprise two main sets of bands
fluorescence of the proligand HL2. At 77 K, vibrational structure (Figure 6 and Table 1). The lower-energy bands can again be
within this band becomes clearly resolved (Figure 5). The attributed to charge-transfer transitions, in line with the well-
intensity distribution of the vibrational components differs for established assignments for cyclometalated iridium complexes
the complex compared to the ligand. The 0,0 band is the most with arylpyridine ligands. They appear at lower energies than the
intense for the complex, whereas the 0,1 band is the most intense corresponding bands in their platinum(II) counterparts but
in the ligand (i.e., the ligand has the larger Huang
Rhys factor), display the same trend to longer wavelengths with extension of
consistent with the higher rigidity expected to be associated with the thiophene chain on going from Ir-1 to Ir-2 to Ir-3.
the metal-bound fluorophore compared to the proligand. A Ir-1 is strongly luminescent in solution. Its emission spec-
reliable value for the lifetime of the lower-energy bands could trum is slightly red shifted compared to that of Pt-1 (0,0 bands
not be obtained due to the low intensity, compounded by the at 564 and 554 nm, respectively), and the vibrational structure
poor sensitivity of the detector in the NIR region. However, these is rather less sharp, which would be consistent with a some-
bands are diminished in intensity in aerated solution, consistent what greater contribution of MLCT character into an other-
with the expectation that they be due to longer-lived phosphor- wise ligand-centered emissive state, Figure 7. In line with
escence from the triplet state, as observed in Pt-1, but substan- this notion is the observation that the luminescence lifetime of
tially red shifted. In summary, Pt-2 displays dual fluorescence and 6.3 μs is significantly shorter than that of Pt-1 (21 μs),
phosphorescence. Apparently, S f T ISC is not fast enough to suggesting that the metal-mediated SOC pathways facilitating
completely eliminate the fluorescence, while the triplet state, triplet radiative decay are more efficient in the iridium
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Inorganic Chemistry ARTICLE

Table 1. Absorption and Emission Data for the Ligands and Their Platinum and Iridium Complexesa

emission 77 K

absorption λmax / nm (ε / μ
1 cm
1) emission λmax / nm τ / ns Φlum  102b λmax/nm τ/ns
1
HL 303 (19 700), 263 (10 400) 351 3.2
HL2 364 (50 600), 256 (15 600) 434 ∼0.5 18 407, 430, 456, 2.1
HL3 400 (79 400), 251 (30 200) 491 <0.5 11 455, 486, 520, 2.4, 0.8 (biexp)
[Pt(L1)(acac)], Pt-1 421 (4640), 403 (5210), 554, 556, 21 000 36 549, 571, 596, 23 000
359 (7480), 332 (18 000), 602, 654 622, 652
316 (17 300), 286 (17 700)

[Pt(L2)(acac)], Pt-2 443 (18 300), 350 (32 600), 495 <0.5 0.58 470, 505, 538 <0.5
295 (16 800) 706, 775 2300 693, 724, 767 not determinable
e e
[Pt(L3)(acac)], Pt-3 458 (29 200), 374 (28 400), 242 (22 500) 525 0.20 497, 532, 568
e d
735
[Ir(L1)2(acac)], Ir-1 463 (6710), 413 (6230), 316 (28 300), 564, 606 6300 46 554, 576, 601, 10 200
282 (33 500) 627, 658
b c c e
[Ir(L2)2(acac)], Ir-2 482 (13 200), 366 (38 000),
333 (33 100), 272 (29 300) 704, 775 1300 0.30 695, 730, 771 1200
e e
[Ir(L3)2(acac)], Ir-3 499 (36 100), 418 (83 900), 247 (45 300) 456, 490, 0.045 405, 428, 457,
519 481, 538
e
793 782 1200
a
In CH2Cl2 except for values at 77 K, which are in diethyl ether/isopentane/ethanol ([Link] v/v). b Where dual emission is observed, the reported values
refer to the total emission quantum yields. c No significant fluorescence. d No clear phosphorescence bands for this complex at 77 K; if present, they are
swamped by the fluorescence. e Emission intensity too weak to record the lifetime.

Figure 4. Absorption spectra of Pt-1, Pt-2, and Pt-3 in CH2Cl2 at

1 2 3 298 ( 3 K.
Figure 3. Fluorescence spectra of HL , HL , and HL in CH2Cl2 at
298 ( 3 K (solid lines) upon excitation into their lowest-energy
absorption bands, and the corresponding spectra at 77 K in a glass of S f T ISC process may be more efficient than in the Pt analogue.
EPA (ether/isopentane/ethanol, [Link] v/v). This conclusion might suggest a greater degree of mixing of metal
orbitals into the frontier orbitals involved in the excitations, a
complex. As for Pt-1, no fluorescence is detectable at higher point we return to below. The spectrum at 77 K is similar to that
energies. at room temperature, but the vibrational structure in the bands
Ir-2 displays a weaker, red-shifted emission compared to Ir-1, becomes more clearly resolved.
emitting in the far red/NIR (λ0,0 = 704 nm; Φ = 0.3  10
2), The terthiophene complex Ir-3 displays dual emission.
with a vibrational spacing similar to that in Ir-1, and a lifetime of A weak, very low-energy band is observed in the NIR
1.3 μs. The logical conclusion is that these bands are due to (λ ≈790 nm). A reliable lifetime could not be obtained at room
phosphorescence from the triplet state, similar to that displayed temperature, but at 77 K, τ = 1.2 μs, consistent with the
by Pt-2. In contrast to Pt-2, however, there is no evidence of any expected phosphorescent origin and red shift compared to
significant fluorescence at higher energies, suggesting that the Ir-2. In contrast to Ir-2, however, Ir-3 also displays a set of

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Inorganic Chemistry ARTICLE

Figure 5. Normalized emission spectra of Pt-1, Pt-2, and Pt-3 in Figure 7. Normalized emission spectra of Ir-1, Ir-2, and Ir-3 in CH2Cl2
CH2Cl2 at 298 ( 3 K upon excitation into the lowest-energy absorption at 298 ( 3 K, and the emission spectrum of Ir-2 at 77 K in EPA (dashed
band in each case. The emission spectrum of Pt-2 at 77 K in EPA is also line). (The sharp, high-energy feature in Ir-3 is a Raman band of the
shown (dashed line). solvent.)

The Pt
N (2.036 Å) and Pt
O bond lengths (2.026
2.123 Å)

are 0.03
0.04 Å longer than the measured values. The calculated
N
Pt
C1 angle (80.8) agrees well with experimental data
(80.9), while the O
Pt
O angle (91.3) is a little smaller than
the experimental one (92.3).14
The optimized ground-state geometry structures of the corre-
sponding model iridium complexes are also shown in Figure 8.
Since no crystal structure of Ir-1 has been reported, we compared
our calculated ground-state geometry of Ir-1 with [Ir(thq)2-
(acac)], where Hthq is 2-thienylquinoline.23 Complex Ir-1
possesses C2 symmetry. Calculated Ir
C bond lengths of
2.004 Å and Ir
O bond lengths of 2.183 Å are overestimated
by about 0.01
0.02 Å in comparison with the measured values,
whereas the Ir
N bond lengths of 2.087 Å are closer to the
experimental values. The calculated N
Ir
C1 angle (80.1)
agrees well with the experimental data (80.1), while the
O
Pt
O angle (85.4) is smaller than the experimental one
Figure 6. Absorption spectra of Ir-1, Ir-2, and Ir-3 in CH2Cl2 at 298 ( 3 K. (86.4). Our data are in good agreement with DFT calculations
published for Ir-1 that employed the B3LYP/LANL2DZ basis
higher-energy fluorescence bands, similar to the dual emission of sets.24
Pt-2 and Pt-3. 6. Molecular Orbitals in the Ground State. Pt Complexes.
In summary, all six complexes display phosphorescence. For Contour plots of the frontier molecular orbitals of the PtII
Pt, the change from one to two thiophenes is accompanied by the complexes in their ground states are shown in Figure 9. The
appearance of an additional fluorescence band, indicating that energies and descriptions of the molecular orbitals, in terms of
the ISC rate is slowed down to a value more comparable to the their % composition of ligand and metal orbitals, are collected in
singlet radiative rate constant, perhaps due to decreasing metal Table S1 in the Supporting Information. An energy level diagram
character in the orbitals. In the case of iridium, this change of the molecular orbitals is presented in Figure 10. For Pt-1, the
appears only upon going from two to three thiophenes. electron density in the HOMO and HOMO
1 orbitals is
5. Computed Geometries. Analogues of the newly obtained delocalized over the thienylpyridine (thpy) and acac ligands
Pt complexes, in which the dodecyl chain is replaced by a and the Pt atom, in which the contributions from metal 5d
hydrogen atom (denoted Pt-20 and Pt-30 ), were used as models orbitals are 23% and 29%, respectively (Table 2). There is
in the calculations in order to reduce the number of atoms and substantial metal
ligand mixing with the π orbitals of the
increase the computational speed. The optimized ground-state ligands. HOMO
2 is mainly based on Pt (93% of 5d con-
geometry structures are shown in Figure 8. Bond lengths and tribution). The LUMO and LUMOþ2 are predominantly
angles at the metal are similar for all three complexes. The localized on the thpy moiety (91%), while LUMOþ1 is shared
calculated ground-state geometrical parameters of Pt-1 are in between thpy and acac ligand π* orbitals (33% and 65%,
good agreement with crystal structural data.14 The calculated respectively). Such MO compositions are typical for cyclometa-
Pt
C bond length of 1.979 Å matches the experimental value. lated Pt complexes with β-diketonato auxiliary ligands.14,25

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Inorganic Chemistry ARTICLE

Figure 8. Optimized geometry structures of the Pt and Ir complexes in their ground states.

Extension of the number of thiophene rings in the ligand with energies and descriptions (% contribution of ligand and
changes quite dramatically the composition of the highest occu- metal orbitals) collected in Table S2 in the Supporting Informa-
pied orbitals in the platinum complexes. In Pt-20 , the HOMO is tion. The electron density in the ground state HOMO of Ir-1 is
predominantly localized on the thpy ligand (90%) with a low localized on the thienylpyridine (thpy) and the Ir atom (36%
contribution of the metal 5d (9%) (Table 2). Incorporation of the contribution from metal 5d; see Table 2), indicating substantial
third thiophene ring in Pt-3 increases the π character of the mixing of the π orbitals of the ligands with the metal. HOMO
1
HOMO up to 95% (only 4% of Pt) and indicates very weak and HOMO
2 are near-degenerate (energy difference is 0.17
metal
ligand mixing in the HOMOs of Pt-20 and Pt-30 . The eV), but they have different character. HOMO
1 has a large
energies of the HOMOs in Pt-20 and Pt-30 rise significantly contribution from the metal (39% Ir 5d), while HOMO
2 is
compared to that of Pt-1 (Table 2, Figure 10), while HOMOs
1 purely a π orbital mainly based on the thienylpyridines (<3%
(with substantial d character, 30% and 28% of the Pt contribution, contribution of 5d). The LUMO and LUMOþ1 are degenerate
respectively, in Pt-20 and Pt-30 ) are less sensitive. Thus, an and predominantly localized on the thpy moieties (88% and 86%,
increase in the π character of the HOMO is also accompanied respectively), i.e., ligand π* orbitals. Similar MO compositions
by increasing the difference between the energies of HOMO and have been calculated for Ir-1 by DFT using the B3LYP/
HOMO
1. The LUMOs in Pt-20 and Pt-30 are localized mainly LANL2DZ level.26
on the o-thpy ligands (95% and 97%). Extension of the conjuga- As in the platinum complexes, extension of the oligothiophene
tion system is thus seen to lead to a clear decrease in the energy chain substantially changes the composition of the highest-
gap between HOMO and LUMO (Figure 10). occupied molecular orbitals in the iridium complexes too. Although
Ir Complexes. Contour plots of the frontier molecular orbitals the energies of the HOMOs in Ir-20 and Ir-30 are not significantly
in the ground states of the Ir complexes are shown in Figure 11, changed compared with Ir-1 (differences < 0.15 eV), the

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Figure 9. Contour plots of the frontier molecular orbitals in the ground state of Pt-1 (left), Pt-20 (center), and Pt-30 (right).

Figure 10. Energy level diagram of the molecular orbitals of the complexes.

Table 2. Calculated Contribution of the Metal in Frontier for Ir-20 and Ir-30 , respectively (Figure 10), such that they have
Molecular Orbitals in the Ground States of the Complexes essentially pure π character (only 3% and 1% of Ir contribution)
and lie close to the HOMO. Indeed, in Ir-30 , HOMO (πd
contribution of the metal in MO (%) character) and HOMO
1 (π character) are almost degenerate.
HOMO
2 HOMO
1 HOMO LUMO
Degenerate LUMOs and LUMOsþ1 in Ir-20 and Ir-30 are
localized mainly on the o-thpy ligands (95% and 97%). As for
Pt-1 92.4 29.4 23.3 7.0 Pt, the extension of the conjugation leads to a significant decrease
Pt-20 42.9 29.7 8.8 4.2 in the energy gap between HOMO and LUMO.
Pt-30 33.7 27.9 4.2 2.5 7. Excitation Energies. Platinum Complexes. The results
Ir-1 2.7 39.2 36.2 4.1 from TD-DFT calculations for Pt-1, Pt-20 , and Pt-30 at optimized
Ir-20 39.2 3.4 25.1 2.8 ground-state geometries are shown in Table S3 in the Supporting
Ir-30 27.8 0.8 16.6 1.5 Information. For each complex, we typically give the vertical
excitation energies for the lowest 10 singlet and 3 triplet states
calculated at the optimized structure for the ground state. The
contributions of metal d orbitals in Ir-2 and Ir-3 are significantly orbitals involved in the dominant excitation process are also
lower (25% and 16%, respectively). The extension of the shown. Energy levels of the lowest singlet and triplet excited
conjugated system increases significantly the energy of the states are shown in Figure 12. For Pt-1, excitation to the lowest
thpy-localized HOMO
1 orbitals up to
5.41 and
5.18 eV triplet state T1 (energy = 2.42 eV) occurs from the HOMO with
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Inorganic Chemistry ARTICLE

Figure 11. Contour plots of frontier orbitals in the ground state for Ir-1 (left), Ir-20 (center), and Ir-30 (right).

πd character to the LUMO with π* character. The correspond- singlet state S1 is about 0.67 eV higher at 2.76 eV, also having
ing singlet state S1 is about 0.67 eV higher at 3.09 eV. The mixed ππ*/MLCT character, as concluded from previous
calculated S0 f S1 absorption is in quite good agreement with calculations.23
the experimental value (difference of 20 nm), which lends Extension of the oligothophene chain leads to a significant
confidence to the calculations and supports the assignment of decrease of the lowest excited states in Ir-20 and Ir-30 compared
the lowest excited states as being of mixed MLCT and ligand- with those of Ir-1. The lowest energy transitions in Ir-20 and Ir-30
centered ππ* (LC) character, as previously described.14 occur from HOMO to LUMO. The low contribution of the
For Pt-20 , the energy of the lowest singlet excited state is metal in the frontier orbitals results in substantial decreasing of
0.23 eV lower than in Pt-1, while the difference between the MLCT character of these transitions, approaching toward essen-
lowest-energy triplet states is more substantial at 0.52 eV. The tially pure ππ* character at Ir-30 .
lowest-energy transitions are again from HOMO to LUMO, 8. Discussion. The presence of a heavy atom, such as platinum
as in Pt-1. However, because of the low contribution of Pt d or iridium, is anticipated to increase spin
orbit coupling and
orbitals in HOMO, we would label the lowest excited state in thus intersystem crossing, provided that its orbitals participate
Pt-20 as ππ* (LC), not MLCT or mixed MLCT/LC. Exten- signficantly in the excited states involved. In small, cyclometa-
sion of the conjugation system in Pt-30 results in a significant lated Pt(II) and Ir(III) complexes, this is typically the case, and
decrease in the S1 and T1 excited state energies (by 0.43 and population of the triplet state from the singlet is favored to such
0.75 eV, respectively), which can also be designated as ππ* an extent that fluorescence cannot compete with ISC (kISC . kf)
because of the very low contribution of the metal in HOMO and no fluorescence is observed. This is the case for Pt-1 and Ir-1.
and LUMO involved in the lowest energy excitations. Calcu- The much lower participation of the metal d orbitals in the
lated absorption spectra of Pt complexes are shown in HOMO in Pt-2 and Pt-3 will render metal
ligand mixing into
Figure 13. the lowest excited states much less efficient, such that the
Iridium Complexes. The results from TD-DFT calculations influence of spin
orbit coupling associated with the heavy atom
for Ir-1, Ir-20 , and Ir-30 are shown in Table S4 in the Supporting will be attenuated. Thus, one may anticipate that the rate of S1 f
Information, where the lowest 10 singlet and 3 triplet states T1 ISC will be reduced, allowing the S1 f S0 radiative process to
calculated at the optimized geometry of the ground state are compete and fluorescence to be observable (kISC ≈ kf). This
given. Energy levels of the lowest singlet and triplet excited states explains the observation of fluorescence in addition to phosphor-
are shown in Figure 14. Calculated absorption spectra of Ir escence in Pt-2 and Pt-3. The increasing energy gap between the
complexes are shown in Figure 15. In Ir-1, excitation to the S1 and the T1 states will also lead to a reduction in the S1 f T1
lowest triplet state T1 (energy = 2.34 eV) can be designated as a rate due to a poorer overlap integral, compounding the above
mixed ππ*/MLCT state from inspection of the orbitals involved effect. Moreover, the inefficient SOC will also mean that the rate
in the transition (HOMO f LUMO). The corresponding of the formally forbidden radiative T1 f S0 process will not be
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Inorganic Chemistry ARTICLE

Figure 12. Energy level diagram of the lowest energy excited states of Pt complexes.

Figure 14. Energy level diagram of the lowest energy excited states of Ir
complexes calculated by TD-DFT.
Figure 13. Simulated absorption spectra of Pt complexes from TD-
DFT.
state (Table S4 in the Supporting Information), and indeed, a
fluorescence band appears in the emission spectrum of this com-
facilitated to the same extent as it was in Pt-1. This is probably a plex too.
key reason why the phosphorescence quantum yields of Pt-2 Comparison of Figure 13 with Figure 4 reveals quite a good
and Pt-3 are so low compared to Pt-1. Nonradiative decay is match between the trends in the calculated and observed
also expected to be increased as the emission energy of Pt-2 and absorption spectra of the platinum complexes. The observed
Pt-3 is substantially lower than Pt-1, in line with the energy red shift with extended conjugation is consistent with the
gap law. decreasing HOMO
LUMO gap calculated. Moreover, as
A somewhat similar trend is observed for the iridium com- noted in section 7, the calculations indicate that the triplet
plexes. However, in this case, there is still sufficient metal state energy drops more rapidly than the singlet state upon
character in the S1 state of Ir-2 (in contrast to Pt-2) to ensure introduction of a second thiophene ring onto the thpy ligand,
that the S1 f T1 process is still much faster than the rate of S1 f and this is reflected in the larger influence on the phosphores-
S0, and no fluorescence is observed. Note that the TD-DFT cence energy (Figure 5 and Table 1) than on the energy of the
calculations designated the S1 state as mixed ππ*/MLCT in Ir-2 lowest-energy absorption band (Figure 4 and Table 1). Analo-
but ππ* in Pt-2 (Tables S4 and S3, respectively, in the Support- gous observations are made for the iridum(III) complexes
ing Information). When Ir-3 is reached, it too has a ππ*-based S1 (Figures 6 and 7).
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Inorganic Chemistry ARTICLE

from petrol ether or DMF. Full synthetic details and characterization are
provided in the Supporting Information.
Preparation of [PtLn(acac)] Complexes. A solution of K2PtCl4 (208
mg, 0.5 mmol) in water (1 mL) was added to a stirred solution of HLn
(0.5 mmol) in acetic acid (30 mL). The mixture was heated at reflux
under nitrogen for 15 h. A precipitated solid of Pt(II) μ-dichloro-bridged
dimer was filtered off, washed with acetic acid (5 mL) and ethanol (5 mL),
and dried in vacuum. The dimer and sodium acetylacetonate (10 equiv)
were heated under reflux in acetone for 16 h. The solvent was removed
under reduced pressure, and the complex was purified by flash chromatog-
raphy (silica gel, DCM eluant). Data for [PtL1(acac)] (Pt-1) was consistent
with that previously reported.13 Full details of the synthesis and character-
ization of Pt-2 and Pt-3 are provided in the Supporting Information.
Preparation of [Ir(Ln)2(acac)] Complexes. The ligand HLn (0.2
mmol), IrCl3 3 xH2O (Ir 55% min, 35 mg, 0.1 mmol), and sodium
acetylacetonate (140 mg, 1 mmol) in a mixture of ethoxyethanol
(30 mL) and water (10 mL) were heated under reflux under nitrogen
for 15 h. The solvent was then removed under reduced pressure, and the
residue was purified by flash chromatography (silica gel, DCM eluant).
Data for [Ir(L1)2(acac)] (Ir-1) were consistent with those previously
Figure 15. Simulated absorption spectra of Ir complexes from TD-DFT. reported.27 Full details of the synthesis and characterization of Ir-2 and
Ir-3 are provided in the Supporting Information.
’ CONCLUSION ii. Instrumentation for Optical Spectroscopy. Absorption
Cyclometalated metal complexes have become central to the spectra were measured on a Biotek Instruments XS spectrometer using
field of the photophysics and photochemistry of coordination quartz cuvettes of 1 cm path length. Steady-state luminescence spectra
complexes and to their application in contemporary technology. were measured using a Jobin Yvon FluoroMax-2 spectrofluorimeter, fitted
The present, systematic study shows that as the size of the with a red-sensitive Hamamatsu R928 photomultiplier tube; the spectra
shown are corrected for the wavelength dependence of the detector, and
conjugated system of the ligand increases, the extent of participa-
the quoted emission maxima refer to the values after correction. Degassing
tion of metal d orbitals in the highest-occupied molecular orbitals
was achieved via a minimum of three freeze
pump
thaw cycles while
decreases. As a result, the influence of the spin
orbit coupling of
connected to the vacuum manifold; the final vapor pressure at 77 K was
the metal in promoting both intersystem crossing, S1 f T1, and <5  10
2 mbar, as monitored using a Pirani gauge. Luminescence
triplet radiative decay, T1 f S0, is attenuated. An increasing quantum yields were determined using [Ru(bpy)3]Cl2 in degassed
S1
T1 energy gap as conjugation increases also has the effect of aqueous solution as the standard, for which Φlum = 0.042;28 estimated
reducing the rate of intersystem crossing. The consequence is uncertainty in Φlum is (20% or better. The luminescence lifetimes of the
that fluorescence becomes observable while the intensity of the complexes were measured by time-correlated single-photon counting
phosphorescence decreases due to the combined effects of a (TCSPC), following excitation at 374.0 nm with an EPL-375 pulsed-
lower yield of triplet formation, a decreased T1 f S0 radiative diode laser. The emitted light was detected at 90 using a Peltier-cooled
decay rate, and increased nonradiative decay as the excited state R928 PMT after passage through a monochromator. The estimated
energy decreases. Clearly, the approach of simply extending the uncertainty in the quoted lifetimes is (10% or better. For Pt-1, the
conjugation in order to obtain more red-shifted emission starts to lifetimes at both 298 and 77 K were independently measured by multi-
break down, a conclusion of particular significance to the design channel scaling using a xenon microsecond flashlamp as the excitation
of technologically relevant NIR-emitting complexes. source in conjunction with an R928 detector.
It can be predicted that for some complexes dual luminescence iii. Computational Methods. For all calculations, the Orca 2.8.0
will be observed, i.e., when the contribution of metal character is package of programs was used.29 In the TD-DFT calculations the B3LYP
still sufficient to promote phosphorescence but not enough for the hybrid functional30,31 was applied. The metals were described by the
ultrafast depletion of the singlet state that normally occurs for Stuttgart
Dresden32 effective core potential (treating the valence
complexes with discrete arylpyridine ligands. Such conclusions are electrons explicitly) using the Ahlrichs def2-TZVP33 basis set of triple-
likely to be quite general, including for metals other than Pt(II) ζ quality. The ground state geometries of the complexes were fully
and Ir(III), but the point at which dual emission is observed may optimized without symmetry constraints at the DFT/B3LYP level using
be dependent on the metal ion (as in the present case of Pt-2 the Ahlrichs double-ζ basis set (VDZ)34 with polarization functions on
compared to Ir-2), according to the efficacy of the SOC pathways. all atoms. To investigate the vertical excitation energies of the low-lying
The current results reinforce the theory that for metals with similar excited states of the complexes, TD-DFT calculations were performed
SOC constants such pathways should be more efficient for using the B3LYP functional together with the Ahlrichs triple-ζ basis set
octahedral d6 complexes than for square-planar d8 complexes.7 with polarization functions on all atoms (TZVP) at the optimized
ground-state (S0) geometry. The COSMO solvation model35 was used
to calculate the solvent effect in DCM (ε = 9.08, nD = 1.424). To
’ EXPERIMENTAL SECTION accelerate TD-DFT calculations we employed the RIJCOSX approx-
I. Synthesis. Typical Procedure for the Stille Coupling. A mixture imation combining the RI-J method and the COSX approximation.36
of 2-bromothienylpyridine 1 or 5 (5.46 mmol), corresponding tribu-
tyltinthiophene 2 or 3 (6.00 mmol), and [Pd(PPh3)4] (0.1 mmol) in dry ’ ASSOCIATED CONTENT
DMF (35 mL) was deaerated by bubbling argon through the mixture,
and then the reaction mixture was stirred for 1 h at 115 C. The solvent bS Supporting Information. Experimental and computa-
was removed under reduced pressure, and the residue was recrystallized tional details and spectral characterization data for new compounds,
3814 [Link]/10.1021/ic200210e |Inorg. Chem. 2011, 50, 3804–3815
Inorganic Chemistry ARTICLE

calculated molecular orbital compositions in the ground states Chi, Y.; Chung, M.-W.; Lin, C.-C. Coord. Chem. Rev. 2011; DOI:
(Tables S1 and S2), excited energies, dominant orbital excitations, 10.1016/[Link].2010.12.013
and oscillator strength (f) from TD-DFT calculations (Tables S3 (12) (a) Wong, W.-Y.; He, Z.; So, S.-K.; Tong, K. L.; Li, Z.
and S4) for the Pt(II) and Ir(III) complexes. This material is Organometallics 2005, 24, 4079–4082. (b) He, Z.; Wong, W.-Y.; Yu,
available free of charge via the Internet at [Link] X.; Kwok, H.-S.; Lin, Z. Inorg. Chem. 2006, 45, 10922–10937.
(13) Grushin, V. V.; Herron, N.; LeCloux, D. D.; Marshall, W. J.;
Petrov, V. A.; Wang, Y. Chem. Commun. 2001, 1494–1495.
’ AUTHOR INFORMATION (14) Brooks, J.; Babayan, Y.; Lamansky, S.; Djurovich, P. I.; Tsyba, I.;
Corresponding Author Bau, R.; Thompson, M. E. Inorg. Chem. 2002, 41, 3055–3066.
(15) (a) Balashev, K. P.; Puzyk, M. V.; Kotlyar, V. S.; Kulikova, M. V.
*E-mail: dnk@[Link] (D.N.K.), [Link]@[Link] Coord. Chem. Rev. 1997, 159, 109–120. (b) Yin, B. L.; Niemeyer, F.;
(D.W.B), [Link]@[Link] (J.A.G.W.). Williams, J. A. G.; Jiang, J.; Boucekkine, A.; Toupet, L.; Le Bozec, H.;
Guerchais, V. Inorg. Chem. 2006, 45, 8584–8596. (c) Niedermair, F.;
’ ACKNOWLEDGMENT Kwon, O.; Zojer, K.; Kappaun, S.; Trimmel, G.; Mereitere, K.; Slugovc,
This work was partly supported by the Russian Foundation for C. Dalton Trans. 2008, 4006–4014. (d) Ghedini, M.; Pugliese, T.; La
Deda, M.; Godbert, N.; Aiello, I.; Amati, M.; Belviso, S.; Lelj, F.; Accorsi,
Basic Researches. D.N.K. and D.W.B. are grateful to The Royal
G.; Barigelletti, F. Dalton Trans. 2008, 4303–4318. (e) Wong, W.-Y.; Ho,
Society for a Joint Project Grant. We are grateful to Johnson C.-L. J. Mater. Chem. 2009, 19, 4457–4482. (f) Liu, J.; Yang, C.-J.; Cao,
Matthey for a generous loan of K2PtCl4. Q.-Y.; Xu, M.; Wang, H.-N.; Peng, J.; Tan, W.-F.; Lue, X.-X.; Gao, X.-C.
Inorg. Chim. Acta 2009, 362, 575–579. (g) Santoro, A.; Whitwood, A. C.;
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