Probes of the metal-to-ligand charge-transfer excited states in ruthenium-Am(m)ine-bipyridine complexes: the effects of NH/ND and CH/CD isotopic substitution on the 77 K luminescence

The effects of ligand perdeuteration on the metal-to-ligand charge-transfer (MLCT) excited-state emission properties at 77 K are described for several [Ru(L)(4)bpy](2+) complexes in which the emission process is nominally [uIII,bpy-] --> [RuII,bpy]. The perdeuteration of the 2,2'-bipyridine (bpy) ligand is found to increase the zero-point energy differences between the ground states and MLCT excited states by amounts that vary from 0 +/- 10 to 70 +/- 10 cm(-1) depending on the ligands L. This indicates that there are some vibrational modes with smaller force constants in the excited states than in the ground states for most of these complexes. These blue shifts increase approximately as the energy difference between the excited and ground states decreases, but they are otherwise not strongly correlated with the number of bipyridine ligands in the complex. Careful comparisons of the [Ru(L)(4)(d(8)-bpy)](2+) and [Ru(L)(4)(h(8)-bpy](2+) emission spectra are used to resolve the very weak vibronic contributions of the C-H stretching modes as the composite contributions of the corresponding vibrational reorganizational energies. The largest of these, 25 +/- 10 cm(-1), is found for the complexes with L = py or bpy/2 and smaller when L = NH(3). Perdeuteration of the am(m)ine ligands (NH(3), en, or [14]aneN(4)) has no significant effect on the zero-point energy difference, and the contributions of the NH stretching vibrational modes to the emission band shape are too weak to resolve. Ligand perdeuteration does increase the excited-state lifetimes by a factor that is roughly proportional to the excited-state-ground-state energy difference, even though the CH and NH vibrational reorganizational energies are too small for nuclear tunneling involving these modes to dominate the relaxation process. It is proposed that metal-ligand skeletal vibrational modes and configurational mixing between metal-centered, bpy-ligand-centered, and MLCT excited states are important in determining the zero-point energy differences, while a large number of different combinations of relatively low-frequency vibrational modes must contribute to the nonradiative relaxation of the MLCT excited states.     

The characterization of the high-frequency vibronic contributions to the 77 K emission spectra of ruthenium-am(m)ine-bipyridyl complexes, their attenuation with decreasing energy gaps, and the implications of strong electronic coupling for inverted-region electron transfer

The 77 K emission spectra of a series of [Ru(Am)6-2n(bpy)n]2+ complexes (n = 1-3) have been determined in order to evaluate the effects of appreciable excited state (e)/ground state (g) configurational mixing on the properties of simple electron-transfer systems. The principal focus is on the vibronic contributions, and the correlated distortions of the bipyridine ligand in the emitting MLCT excited state. To address the issues that are involved, the emission band shape at 77 K is interpreted as the sum of a fundamental component, corresponding to the {e,0'} --> {g,0} transition, and progressions in the ground-state vibrational modes that correlate with the excited-state distortion. Literature values of the vibrational parameters determined from the resonance-Raman (rR) for [Ru(NH3)4bpy]2+ and [Ru(bpy)3]2+ are used to model the emission spectra and to evaluate the spectral analysis. The Gaussian fundamental component with an energy Ef and bandwidth Deltanu1/2 is deconvoluted from the observed emission spectrum. The first-, second-, and third-order terms in the progressions of the vibrational modes that contribute to the band shape are evaluated as the sums of Gaussian-shaped contributions of width Deltanu1/2. The fundamental and the rR parameters give an excellent fit of the observed emission spectrum of [Ru(NH3)4bpy]2+, but not as good for the [Ru(bpy)3]2+ emission spectrum probably because the Franck-Condon excited state probed by the rR is different in symmetry from the emitting MLCT excited state. Variations in vibronic contributions for the series of complexes are evaluated in terms of reorganizational energy profiles (emreps, Lambdax) derived from the observed spectra, and modeled using the rR parameters. This modeling demonstrates that most of the intensity of the vibronic envelopes obtained from the frozen solution emission spectra arises from the overlapping of first-order vibronic contributions of significant bandwidth with additional convoluted contributions of higher order vibronic terms. The emrep amplitudes of these complexes have their maxima at about 1500 cm(-1) in frozen solution, and Lambdax(max) decreases systematically by approximately 2-fold as Ef decreases from 17,220 for [Ru(bpy)3]2+ to 12,040 cm(-1) for [Ru(NH3)4bpy]2+ through the series of complexes. Corrections for higher order contributions and bandwidth differences based on the modeling with rR parameters indicate that the variations in Lambdax(max) imply somewhat larger decreases in first-order bpy vibrational reorganizational energies. The large attenuation of vibrational reorganizational energies of the [Ru(Am)6-2n(bpy)n]2+ complexes contrasts with the apparent similarity of reorganizational energy amplitudes for the absorption and emission of [Ru(NH3)4bpy]2+. These observations are consistent with increasing and very substantial excited-state/ground-state configurational mixing and decreasing excited-state distortion as Ef decreases, but more severe attenuation for singlet/singlet than triplet/singlet mixing (alphage > alphaeg for the configurational mixing coefficients at the ground-state and excited-state potential energy minima, respectively); it is inferred that 0.18 > or = alphage2 > or = 0.09 for [Ru(bpy)3]2+ and 0.37 > or = alphage2 > or = 0.18 for [Ru(NH3)4bpy]2+ in DMSO/water glasses, where the ranges are based on models that there is or is not a spin restriction on configurational mixing (alphage > alphaeg and alphage = alphaeg), respectively, for these complexes.     

Effects of excited state-excited state configurational mixing on emission bandshape variations in ruthenium-bipyridine complexes

The 77 K emission spectra of 21 [Ru(L) 4bpy] ( m+ ) complexes for which the Ru/bpy metal-to-ligand-charge-transfer ( (3)MLCT) excited-state energies vary from 12 500 to 18 500 cm (-1) have vibronic contributions to their bandshapes that implicate excited-state distortions in low frequency ( lf; hnu lf < 1000 cm (-1)), largely metal-ligand vibrational modes which most likely result from configurational mixing between the (3)MLCT and a higher energy metal centered ( (3)LF) excited state. The amplitudes of the lf vibronic contributions are often comparable to, or sometimes greater than those of medium frequency ( mf; hnu mf > 1000 cm (-1)), largely bipyridine (bpy) vibrational modes, and for the [Ru(bpy) 3] (2+) and [Ru(NH 3) 4bpy] (2+) complexes they are consistent with previously reported resonance-Raman (rR) parameters. However, far smaller lf vibronic amplitudes in the rR parameters have been reported for [Os(bpy) 3 ] (2+), and this leads to a group frequency approach for interpreting the 77 K emission bandshapes of [Ru(L) 4bpy] ( m+ ) complexes with the vibronic contributions from mf vibrational modes referenced to the [Os(bpy) 3] (2+) rR parameters (OB3 model) and the envelope of lf vibronic components represented by a "progression" in an "equivalent" single vibrational mode ( lf1 model). The lf1 model is referenced to rR parameters reported for [Ru(NH 3) 4bpy] (2+). The observation of lf vibronic components indicates that the MLCT excited-state potential energy surfaces of Ru-bpy complexes are distorted by LF/MLCT excited-state/excited-state configurational mixing, but the emission spectra only probe the region near the (3)MLCT potential energy minimum, and the mixing can lead to larger distortions elsewhere with potential photochemical implications: (a) such distortions may labilize the (3)MLCT excited state; and (b) the lf vibrational modes may contribute to a temperature dependent pathway for nonradiative relaxation.     

Contrasts in the 77 K emission spectra, structures, and dynamics of metal-to-metal and metal-to-ligand charge-transfer excited states

The 77 K emission spectrum of trans-[(ms-Me6[14]aneN4)Cr(CNRu(NH3)5)2]5+ has components characteristic of ligand field (LF) and metal-to-metal charge transfer (MMCT) excited states (ms-Me6[14]aneN4=5,12-meso-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). The LF component of the emission is best resolved for irradiations at appreciably higher energies than the MMCT absorption band, while only the MMCT emission is observed for irradiations on the low-energy side of the MMCT absorption band. The LF emission component from this complex has vibronic structure that is very similar to that of the trans-[(ms-Me6[14]aneN4)Cr(CN)2]+ parent, but it is red-shifted by 560 cm-1 and the bandwidths are much larger. The red shift and the larger bandwidths of the ruthenated complex are attributed to configurational mixing between the LF and MMCT excited states, and the inferred mixing parameters are shown to be consistent with the known electron-transfer properties of the Ru(NH3)5 moieties. The MMCT excited-state lifetime is about 1 micros at 77 K and am(m)ine perdeuteration of this complex leads to an isotope effect of kNH/kND approximately 15-20. However, the contribution of the N-H stretching vibration to the emission sideband is too weak for a single vibrational mode model to be consistent with the observed lifetimes or the isotope effect. These features are very similar to those reported previously (J. Phys. Chem. A 2004, 108, 5041) for the MMCT emission of trans-[([14]aneN4)Cr{CNRu(NH3)5}2]5+ ([14]aneN4=1,4,8,11-tetraazacyclotetradecane), with the exception that the higher energy LF emission was not well resolved in the earlier work. The energies of the charge transfer absorption and emission maxima of both of these Cr(CN)Ru complexes are very similar to those of [Ru(NH3)4bpy]2+, but the latter has a 50-fold shorter 77 K excited-state lifetime, a 10-fold smaller NH/ND isotope effect, and a very different structure of its vibronic sidebands. Thus, the vibronic sidebands imply that the dominant excited-state distortions are in the metal-ligand vibrational modes for the Cr(CN)Ru complexes and in the bipyridine vibrational modes for the [Ru(NH3)4bpy]2+ complex. While an "equivalent" single vibrational mode model based on the frequencies and amplitudes of the dominant distortion modes is not consistent the observed lifetimes, such models do appear to be a good basis for qualitatively distinguishing different classes of excited-state dynamic behavior. A multimode, multichannel model may be necessary to adequately describe the excited-state dynamics of these simple electron-transfer systems.     

Characteristics and properties of metal-to-ligand charge-transfer excited states in 2,3-bis(2-pyridyl)pyrazine and 2,2'-bypyridine ruthenium complexes. Perturbation-theory-based correlations of optical absorption and emission parameters with electrochemistry and thermal kinetics and related Ab initio calculations

The absorption, emission, and infrared spectra, metal (Ru) and ligand (PP) half-wave potentials, and ab initio calculations on the ligands (PP) are compared for several [L(n)()Ru(PP)](2+) and [[L(n)Ru]dpp[RuL'(n)]](4+) complexes, where L(n) and L'(n) = (bpy)(2) or (NH(3))(4) and PP = 2,2'-bipyridine (bpy), 2,3-bis(2-pyridyl)pyrazine (dpp), 2,3-bis(2-pyridyl)quinoxaline (dpq), or 2,3-bis(2pyridyl)benzoquinoxaline (dpb). The energy of the metal-to-ligand charge-transfer (MLCT) absorption maximum (hnu(max)) varies in nearly direct proportion to the difference between Ru(III)/Ru(II) and (PP)/(PP)(-) half-wave potentials, DeltaE(1/2), for the monometallic complexes but not for the bimetallic complexes. The MLCT spectra of [(NH(3))(4)Ru(dpp)](2+) exhibit three prominent visible-near-UV absorptions, compared to two for [(NH(3))(4)Ru(bpy)](2+), and are not easily reconciled with the MLCT spectra of [[(NH(3))(4)Ru]dpp[RuL(n)]](4+). The ab initio calculations indicate that the two lowest energy pi orbitals are not much different in energy in the PP ligands (they correlate with the degenerate pi orbitals of benzene) and that both contribute to the observed MLCT transitions. The LUMO energies calculated for the monometallic complexes correlate strongly with the observed hnu(max) (corrected for variations in metal contribution). The LUMO computed for dpp correlates with LUMO + 1 of pyrazine. This inversion of the order of the two lowest energy pi orbitals is unique to dpp in this series of ligands. Configurational mixing of the ground and MLCT excited states is treated as a small perturbation of the overall energies of the metal complexes, resulting in a contribution epsilon(s) to the ground-state energy. The fraction of charge delocalized, alpha(DA)(2), is expected to attenuate the reorganizational energy, chi(reorg), by a factor of approximately (1 - 4alpha(DA)(2) + alpha(DA)(4)), relative to the limit where there is no charge delocalization. This appears to be a substantial effect for these complexes (alpha(DA)(2) congruent with 0.1 for Ru(II)/bpy), and it leads to smaller reorganizational energies for emission than for absorption. Reorganizational energies are inferred from the bandwidths found in Gaussian analyses of the emission and/or absorption spectra. Exchange energies are estimated from the Stokes shifts combined with perturbation--theory-based relationship between the reorganizational energies for absorption and emission values. The results indicate that epsilon(s) is dominated by terms that contribute to electron delocalization between metal and PP ligand. This inference is supported by the large shifts in the N-H stretching frequency of coordinated NH(3) as the number of PP ligands is increased. The measured properties of the bpy and dpp ligands seem to be very similar, but electron delocalization appears to be slightly larger (10-40%) and the exchange energy contributions appear to be comparable (e.g., approximately 1.7 x 10(3) cm(-1) in [Ru(bpy)(2)dpp](2+) compared to approximately 1.3 x 10(3) cm(-1) in the bpy analogue).     

Photophysical properties of ligand localized excited state in ruthenium(II) polypyridyl complexes: a combined effect of electron donor-acceptor ligand

We have synthesized ruthenium(II) polypyridyl complexes (1) Ru(II)(bpy)(2)(L(1)), (2) Ru(II)(bpy)(2)(L(2)) and (3) Ru(II)(bpy)(L(1))(L(2)), where bpy = 2,2'-bipyridyl, L(1) = 4-[2-(4'-methyl-2,2'-bipyridinyl-4-yl)vinyl]benzene-1,2-diol) and L(2) = 4-(N,N-dimethylamino-phenyl)-(2,2'-bipyridine) and investigated the intra-ligand charge transfer (ILCT) and ligand-ligand charge transfer (LLCT) states by optical absorption and emission studies. Our studies show that the presence of electron donating -NMe(2) functionality in L(2) and electron withdrawing catechol fragment in L(1) ligands of complex 3 introduces low energy LLCT excited states to aboriginal MLCT states. The superimposed LLCT and MLCT state produces redshift and broadening in the optical absorption spectra of complex 3 in comparison to complexes 1 and 2. The emission quantum yield of complex 3 is observed to be extremely low in comparison to that of complex 1 and 2 at room temperature. This is attributed to quenching of the (3)MLCT state by the low-emissive (3)LLCT state. The emission due to ligand localized CT state (ILCT and LLCT) of complexes 2 and 3 is revealed at 77 K in the form of a new luminescence band which appeared in the 670-760 nm region. The LLCT excited state of complex 3 is populated either via direct photoexcitation in the LLCT absorption band (350-700 nm) or through internal conversion from the photoexcited (3)MLCT (400-600 nm) states. The internal conversion rate is determined by quenching of the (3)MLCT state in a time resolved emission study. The internal conversion to LLCT and ILCT excited states are observed to be as fast as ～200 ps and ～700 ps for complexes 3 and 2, respectively. The present study illustrates the photophysical property of the ligand localized excited state of newly synthesized heteroleptic ruthenium(II) polypyridyl complexes.     

The Early Picosecond Photophysics of Ru(II) Polypyridyl Complexes: A Tale of Two Timescales

The early picosecond time scale excited-state dynamics of the paradigm tris(2,2'-bipyridyl)Ruthenium(II) ([Ru(bpy)(3)](2+)) and related complexes have been examined by picosecond Kerr-gated time-resolved resonance Raman (ps-TR(3)) spectroscopy. The evolution of the signature Raman bands of the lowest thermally equilibrated excited (THEXI) state under two-color pump/probe conditions show that this state is not fully populated within several hundred femtoseconds as proposed previously but rather only within the first 20 ps following excitation. In addition to an emission observed within the instrument rise time (τ < 3 ps), the early picosecond dynamics are characterized by a rise in the intensity of the Raman marker bands of the THEXI-(3)MLCT state, a rise time which, within experimental uncertainty, is not influenced by either partial or complete ligand deuteriation or the presence of ligands other than bpy, as in the heteroleptic complexes [Ru(bpy)(2)(L1)](+) and [Ru(bpy)(2)(Hdcb)](+) (where H(2)dcb is 4,4'-dicarboxy-2,2'-bipyridine and L1 is 2,-(5'-phenyl-4'-[1,2,4]triazole-3'-yl)pyridine). Overall, although the results obtained in the present study are consistent with those obtained from examination of this paradigm complex on the femtosecond timescale, regarding initial formation of the vibrationally hot (3)MLCT state by ISC from the singlet Franck-Condon state, the observation that the THEXI-(3)MLCT state reaches thermal equilibration over a much longer time period than previously suggested warrants a re-examination of views concerning the rapidity with which thermal equilibration of transition metal complex excited states takes place.     

Probing the excited states of Ru(II) complexes with dipyrido[2,3-a:3',2'-c]phenazine: a transient resonance raman spectroscopy and computational study

The lifetimes and transient resonance Raman spectra for Ru(II) complexes with the dipyrido[2,3-a:3',2'-c]phenazine (ppb) ligand and substituted analogues have been measured. The effect of altering the Ru(II) center ([Ru(CN)4]2- versus [Ru(bpy)2]2+), of the complex, on the excited-state lifetimes and spectra has been considered. For [Ru(bpy)2L]2+ complexes the excited-state lifetimes range from 124 to 600 ns in MeCN depending on the substituents on the ppb ligand. For the [Ru(CN)4L]2- complexes the lifetimes in H2O are approximately 5 ns. The transient resonance Raman spectra for the MLCT excited states of these complexes have been measured. The data are analyzed by comparison with the resonance Raman spectra of the electrochemically reduced [(PPh3)2Cu(mu-L*-)Cu(PPh3)2]+ complexes. The vibrational spectra of the complexes have been modeled using DFT methods. For experimental ground-state vibrational spectra of the complexes the data may be compared to calculated spectra of the ligand or metal complex. It is found that the mean absolute deviation between experimental and calculated frequencies is less for the calculation on the respective metal complexes than for the ligand. For the transient resonance Raman spectra of the complexes the observed vibrational bands may be compared with those of the calculated ligand radical anion, the reduced complex [Ru(CN)4L*-]3-, or the triplet state of the complex. In terms of a correlation with the observed transient RR spectra, calculations on the metal complex models offered no significant improvement compared to those based on the ligand radical anion alone. In all cases small structural changes are predicted on going from the ground to excited state.     

Picosecond isomerization in photochromic ruthenium-dimethyl sulfoxide complexes

The complexes [Ru(tpy)(bpy)(dmso)](OSO(2)CF(3))(2) and trans-[Ru(tpy)(pic)(dmso)](PF(6)) (tpy is 2,2':6',2' '-terpyridine, bpy is 2,2'-bipyridine, pic is 2-pyridinecarboxylate, and dmso is dimethyl sulfoxide) were investigated by picosecond transient absorption spectroscopy in order to monitor excited-state intramolecular S-->O isomerization of the bound dmso ligand. For [Ru(tpy)(bpy)(dmso)](2+), global analysis of the spectra reveals changes that are fit by a biexponential decay with time constants of 2.4 +/- 0.2 and 36 +/- 0.2 ps. The first time constant is assigned to relaxation of the S-bonded (3)MLCT excited state. The second time constant represents both excited-state relaxation to ground state and excited-state isomerization to form O-[Ru(tpy)(bpy)(dmso)](2+). In conjunction with the S-->O isomerization quantum yield (Phi(S)(-->)(O) = 0.024), isomerization of [Ru(tpy)(bpy)(dmso)](2+) occurs with a time constant of 1.5 ns. For trans-[Ru(tpy)(pic)(dmso)](+), global analysis of the transient spectra reveals time constants of 3.6 +/- 0.2 and 118 +/- 2 ps associated with these two processes. In conjunction with the S-->O isomerization quantum yield (Phi(S)(-->)(O) = 0.25), isomerization of trans-[Ru(tpy)(pic)(dmso)](+) occurs with a time constant of 480 ps. In both cases, the thermally relaxed excited states are assigned as terpyridine-localized (3)MLCT states. Electronic state diagrams are compiled employing these data as well as electrochemical, absorption, and emission data to describe the reactivity of these complexes. The data illustrate that rapid bond-breaking and bond-making reactions can occur from (3)MLCT excited states formed from visible light irradiation.     

Modulation of the lowest metal-to-ligand charge-transfer state in [Ru(bpy)2(N-N)]2+ systems by changing the N-N from hydrazone to azine: photophysical consequences

Two Ru(II) complexes, [Ru(bpy)2L](ClO4)2 (1) and [Ru(bpy)2L'](BF4)2 (2), where bpy is 2,2'-bipyridine, L is diacetyl dihydrazone, and L' 1:2 is the condensate of L and acetone, are synthesized. From X-ray crystal structures, both are found to contain distorted octahedral RuN(6)(2+) cores. NMR spectra show that the cations in 1 and 2 possess a C2 axis in solution. They display the expected metal-to-ligand charge transfer (1MLCT) band in the 400-500 nm region. Complex 1 is nonemissive at room temperature in solution as well as at 80 K. In contrast, complex 2 gives rise to an appreciable emission upon excitation at 440 nm. The room-temperature emission is centered at 730 nm (lambda(em)(max)) with a quantum yield (Phi(em)) of 0.002 and a lifetime (tau(em)) of 42 ns in an air-equilibrated methanol-ethanol solution. At 80 K, Phi(em) = 0.007 and tau(em) = 178 ns, with a lambda(em)(max) of 690 nm, which is close to the 0-0 transition, indicating an 3MLCT excited-state energy of 1.80 eV. The radiative rate constant (5 x 10(4) s(-1)) at room temperature and 80 K is almost temperature independent. From spectroelectrochemistry, it is found that bpy is easiest to reduce in 2 and that L is easiest in 1. The implications of this are that in 2 the lowest (3)MLCT state is localized on a bpy ligand and in 1 it is localized on L. Transient absorption results also support these assignments. As a consequence, even though 2 shows a fairly strong and long-lived emission from a Ru(II) --> bpy CT state, the Ru(II) --> L CT state in 1 shows no detectable emission even at 80 K.     

Photophysical properties of ruthenium bipyridine (4-carboxylic acid-4'-methyl-2,2'-bipyridine) complexes and their acid-base chemistry

Photophysical properties such as absorption and emission spectra, lifetimes, and redox potentials of eight ruthenium complexes, Ru(LL)2(MebpyCOOH)2+, where LL represents bpy, phen, Me2bpy, Me4bpy, (MeO)2bpy, (EtO)2bpy, Cl2bpy, and NO2phen, have been measured. The acid dissociation constants of ground and excited states have been determined. The ground-state pKa values were obtained from the pH dependence of the complex absorbance changes. The excited-state pKa* values were extracted from the emission titration curve and corrected for the excited-state lifetime of both protonated and deprotonated species. The largest DeltapKa, pKa*-pKa, found for Ru(Me2bpy)2(MebpyCOOH)2+ and Ru(Me4bpy)2(MebpyCOOH)2+ of 1.7 indicate that MebpyCOOH gains most of the MLCT excited-state electron. The big negative DeltapKa found for Ru(Cl2bpy)2(MebpyCOOH)2+, -4.2, clearly indicates the metal-to-ligand charge transfer to the Cl2bpy ligands.     

New Ru(II) chromophores with extended excited-state lifetimes

We describe the synthesis, electrochemical, and photophysical properties of two new luminescent Ru(II) diimine complexes covalently attached to one and three 4-piperidinyl-1,8-naphthalimide (PNI) chromophores, [Ru(bpy)(2)(PNI-phen)](PF(6))(2) and [Ru(PNI-phen)(3)](PF(6))(2), respectively. These compounds represent a new class of visible light-harvesting Ru(II) chromophores that exhibit greatly enhanced room-temperature metal-to-ligand charge transfer (MLCT) emission lifetimes as a result of intervening intraligand triplet states ((3)IL) present on the pendant naphthalimide chromophore(s). In both Ru(II) complexes, the intense singlet fluorescence of the pendant PNI chromophore(s) is nearly quantitatively quenched and was found to sensitize the MLCT-based photoluminescence. Excitation into either the (1)IL or (1)MLCT absorption bands results in the formation of both (3)MLCT and (3)IL excited states, conveniently monitored by transient absorption and fluorescence spectroscopy. The relative energy ordering of these triplet states was determined using time-resolved emission spectra at 77 K in an EtOH/MeOH glass where dual emission from both Ru(II) complexes was observed. Here, the shorter-lived higher energy emission has a spectral profile consistent with that typically observed from (3)MLCT excited states, whereas the millisecond lifetime lower energy band was attributed to (3)IL phosphorescence of the PNI chromophore. At room temperature the data are consistent with an excited-state equilibrium between the higher energy (3)MLCT states and the lower energy (3)PNI states. Both complexes display MLCT-based emission with room-temperature lifetimes that range from 16 to 115 micros depending upon solvent and the number of PNI chromophores present. At 77 K it is apparent that the two triplet states are no longer in thermal equilibrium and independently decay to the ground state.     

Synthesis and spectroscopic characterization of CN-substituted bipyridyl complexes of Ru(II)

A series of ruthenium complexes having the general form [Ru(bpy)(3-n)(CN-Me-bpy)(n)](PF(6))(2) (where bpy = 2,2'-bipyridine, CN-Me-bpy = 4,4'-dicyano-5,5'-dimethyl-2,2'-bipyridine, and n = 1-3 for complexes 1-3, respectively) have been synthesized and characterized using a variety of steady-state and nanosecond time-resolved spectroscopies. Electrochemical measurements indicate that the CN-Me-bpy ligand is significantly easier to reduce than the unsubstituted bipyridine (on the order of ～500 mV), implying that the lowest energy (3)MLCT (metal-to-ligand charge transfer) state will be associated with the CN-Me-bpy ligand(s) in all three compounds. Comparison of the Huang-Rhys factors derived from spectral fitting analyses of the steady state emission spectra of complexes 1-3 suggests all three compounds are characterized by excited-state geometries that are less distorted relative to their ground states as compared to [Ru(bpy)(3)](PF(6))(2); the effect of the more nested ground- and excited-state potentials is reflected in the unusually high radiative quantum yields (13% (1), 27% (2), and 40% (3)) and long (3)MLCT-state room-temperature lifetimes (1.6 μs, 2.6 μs, and 3.5 μs, respectively) for these compounds. Coupling of the π* system into the CN groups is confirmed by nanosecond step-scan IR spectra which reveal a ～40 cm(-1) bathochromic shift of the CN stretching frequency, indicative of a weaker CN bond in the (3)MLCT excited state relative to the ground state. The fact that the shift is the same for complexes 1-3 is evidence that, in all three complexes, the long-lived excited state is localized on a single CN-Me-bpy ligand rather than being delocalized over multiple ligands.     

Ultrafast photochemical dissociation of an equatorial CO ligand from trans(X,X)-[Ru(X)2(CO)2(bpy)] (X = Cl, Br, I): a picosecond time-resolved infrared spectroscopic and DFT computational study

Ultrafast photochemistry of the complexes trans(X,X)-[Ru(X)(2)(CO)(2)(bpy)] (X = Cl, Br, I) was studied in order to understand excited-state reactivity of equatorial CO ligands, coordinated trans to the 2,2'-bipyridine ligand (bpy). TD-DFT calculations have identified the lowest electronic transitions and singlet excited states as mixed X -->bpy/Ru --> bpy ligand to ligand/metal to ligand charge transfer (LLCT/MLCT). Picosecond time-resolved IR spectroscopy in the region of nu(CO) vibrations has revealed that, for X = Cl and Br, subpicosecond CO dissociation is accompanied by bending of the X-Ru-X moiety, producing a pentacoordinated intermediate trans(X,X)-[Ru(X)(2)(CO)(bpy)]. Final movement of an axial halide ligand to the vacant equatorial position and solvent (CH(3)CN) coordination follows with a time constant of 13-15 ps, forming the photoproduct cis(X,X)-[Ru(X)(2)(CO)(CH(3)CN)(bpy)]. For X = I, the optically populated (1)LLCT/MLCT excited state undergoes a simultaneous subpicosecond CO dissociation and relaxation to a triplet IRuI-localized excited state which involves population of an orbital that is sigma-antibonding with respect to the axial I-Ru-I bonds. Vibrationally relaxed photoproduct cis(I,I)-[Ru(I)(2)(CO)(CH(3)CN)(bpy)] is formed with a time constant of ca. 55 ps. The triplet excited state is unreactive, decaying to the ground state with a 155 ps lifetime. The experimentally observed photochemical intermediates and excited states were assigned by comparing calculated (DFT) and experimental IR spectra. The different behavior of the chloro and bromo complexes from that of the iodo complex is caused by different characters of the lowest triplet excited states.     

Dual emission from 3MLCT and 3ILCT excited states in a new Ru(II) diimine complex

The unique behavior of a new Ru(II) diimine complex, Ru(bpy)(2)(L)(2+) (where L is 4-methyl-4'-[p-(dimethyl- amino)-alpha-styryl]-2,2'-bipyridine, bpy is 2,2'-bipyridine), was studied in detail. Due to the strong electron donating property of the amino group, an ILCT (intraligand charge transfer) state is involved either in the absorption spectra or in the time-resolved emission spectra. Dual emission based on (3)MLCT and (3)ILCT states was observed at room temperature for the first time via a time-resolved technique in Ru(II) diimine complexes.     

Synthesis and characterization of ruthenium(II) molecular assemblies for photosensitization of nanocrystalline TiO2: utilization of hydroxyl grafting mode

New Ru polypyridine complexes [(bpy)2Ru(L)]2+, where bpy = 2,2'-bipyridine and L = dipyrido[3,2-a:2',3'-c]-phenazine-2-carboxylic acid (dppzc), dipyrido[3,2-f:2',3'-h]quinoxaline-2,3-dicarboxylic acid (dpq(COOH)2), 3-hydroxydipyrido[3,2-f:2',3'-h]quinoxaline-2-carboxylic acid (dpq(OHCOOH)), 2,3-dihydroxydipyrido[3,2-f:2',3'-h]quinoxaline (dpq(OH)2), and [(L')Ru(dppzc)2]2+, where L' = bpy and 1,10-phenanthroline (phen), have been synthesized, characterized, and anchored to nanocrystalline TiO2 electrodes for light to electrical energy conversion in regenerative photoelectrochemical cells with I-/I2 acetonitrile electrolyte. These sensitizers have intense metal-to-ligand charge-transfer (MLCT) bands centered at approximately 450 nm. The effect of pH on the absorption and emission spectra of these complexes consisting of protonatable ligands has been investigated in water by spectrophotometric titration. The excited-state pKa values are more basic than the ground-state ones, except the pKa2 and pKa2* in [(bpy)2Ru(dpq(OH)2)]2+, which are equal, suggesting the localization of the lowest-energy MLCT on heteroaromatic bridging ligands, dppzc and dpq. Incident photon-to-current conversion efficiency (IPCE) is sensitive to the structural changes that resulted from introducing different functional groups, used for grafting.     

Changing the role of 2,2'-bipyridine from secondary ligand to protagonist in [Ru(bpy)2(N-N)]2+ complexes: low-energy, red emission from a ruthenium(II)-to-2,2'-bipyridine 3MLCT state

Two new bidentate ligands (1 and 2) with bicyclic guanidine moieties were synthesized and attached to a Ru(II)(bpy)(2) core (bpy = 2,2'-bipyridine) to afford complexes 3 and 4, which were characterized by spectroscopic and electrochemical methods. Complex 4 was further characterized by X-ray crystallography. In cyclic voltammetric studies, both complexes show a Ru(II/III) couple, which is 500 mV less positive than the Ru(II/III) couple of Ru(bpy)(3)(2+). The (1)MLCT and (3)MLCT states of 3 (560 nm/745 nm) and 4 (550 nm/740 nm) are significantly red-shifted with respect to Ru(bpy)(3)(2+) (440 nm/620 nm). Compounds 3 and 4 exhibit emission from a Ru(II)-to-bpy (3)MLCT state, which is rarely the emitting state at λ > 700 nm in [Ru(bpy)(2)(N-N)](2+) complexes.     

Syntheses and properties of emissive iridium(III) complexes with tridentate benzimidazole derivatives

A series of novel emissive Ir(III) complexes having the coordination environments of [Ir(N--N--N)2]3+, [Ir(N--N--N)(N--N)Cl]2+, and [Ir(N--N--N)(N--C--N)]2+ with 2,6-bis(1-methyl-benzimidazol-2-yl)pyridine (L1, N--N--N), 1,3-bis(1-methyl-benzimidazol-2-yl)benzene (L2H, N--C--N), 4'-(4-methylphenyl)-2,2':6',2' '-terpyridine (ttpy, N--N--N), and 2,2'-bipyridine (bpy, N--N) have been synthesized and their photophysical and electrochemical properties studied. The Ir(III) complexes exhibited phosphorescent emissions in the 500-600 nm region, with lifetimes ranging from approximately 1-10 micros at 295 K. Analysis of the 0-0 energies and the redox potentials indicated that the lowest excited state of [Ir(L1)(L2)]2+ possessed the highest contribution of 3MLCT (MLCT = metal-to-ligand charge transfer) among the Ir(III) complexes, reflecting the sigma-donating ability of the tridentate ligand, ttpy < L1 < L2. The emission quantum yields (phi) of the Ir(III) complexes ranged from 0.037 to 0.19, and the highest phi value (0.19) was obtained for [Ir(L1)(bpy)Cl]2+. Radiative rate constants (k(r)) were 1.2 x 10(4) s(-1) for [Ir(ttpy)2]3+, 3.7 x 10(4) s(-1) for [Ir(L1)(bpy)Cl]2+, 3.8 x 10(4) s(-1) for [Ir(ttpy)(bpy)Cl]2+, 3.9 x 10(4) s(-1) for [Ir(L1)2]3+, and 6.6 x 10(4) s(-1) for [Ir(L1)(L2)]2+. The highest radiative rate for [Ir(L1)(L2)]2+ with the highest contribution of 3MLCT could be explained in terms of the singlet-triplet mixing induced by spin-orbit coupling of 5d electrons in the MLCT electronic configurations.     

Role of electronic structure on DNA light-switch behavior of Ru(II) intercalators

A series of ruthenium(II) complexes possessing ligands with an extended pi system were synthesized and characterized. The complexes are derived from [Ru(bpy)3](2+) (1, bpy = 2,2'-bipyridine) and include [Ru(bpy)2(tpphz)](2+) (2, tpphz = tetrapyrido[3,2-a:2',3'-c:3',2'-h:2',3'-j]phenazine), [Ru(bpy)2(dppx)](2+) (3, dppx = 7,8-dimethyldipyrido[3,2-a:2',3'-c]phenazine), [Ru(bpy)2(dppm2)](2+) (4, dppm2 = 6-methyldipyrido[3,2-a:2',3'-c]phenazine), and [Ru(bpy)2(dppp2)](2+) (5, dppp2 = pyrido[2',3':5,6]pyrazino[2,3-f][1,10]phenanthroline). The excited-state properties of these complexes, including their DNA "light-switch" behavior, were compared to those of [Ru(bpy)2(dppz)](2+) (6, dppz = dipyrido[3,2-a:2',3'-c]phenazine). Whereas 2, 3, and 4 can be classified as DNA light-switch complexes, 5 exhibits negligible luminescence enhancement in the presence of DNA. Because relative viscosity experiments show that 2-6 bind to DNA by intercalation, their electronic absorption and emission spectra, electrochemistry, and temperature dependence of the luminescence were used to explain the observed differences. The small energy gap between the lowest-lying dark excited state and the bright state in 2-4 and 6 is related to the ability of these complexes to exhibit DNA light-switch behavior, whereas the large energy gap in 5 precludes the emission enhancement in the presence of DNA. The effect of the energy gap among low-lying states on the photophysical properties of 1-6 is discussed. In addition, DFT and TD-DFT calculations support the conclusions from the experiments.     

Tuning the excited-state properties of [M(SnR3)2(CO)2(alpha-diimine)] (M = Ru, Os; R = Me, Ph)

The influences of R, the alpha-diimine, and the transition metal M on the excited-state properties of the complexes [M(SnR3)2(CO)2(alpha-diimine)] (M = Ru, Os; R = Ph, Me) have been investigated. Various synthetic routes were used to prepare the complexes, which all possess an intense sigma-bond-to-ligand charge-transfer transition in the visible region between a sigma(Sn-M-Sn) and a pi*(alpha-diimine) orbital. The resonance Raman spectra show that many bonds are only weakly affected by this transition. The room-temperature time-resolved absorption spectra of [M(SnR3)2(CO)2(dmb)] (M = Ru, Os; R = Me, Ph; dmb = 4,4'-dimethyl-2,2'-bipyridine) show the absorptions of the radical anion of dmb, in line with the SBLCT character of the lowest excited state. The excited-state lifetimes at room temperature vary between 0.5 and 3.6 microseconds and are mainly determined by the photolability of the complexes. All complexes are photostable in a glass at 80 K, under which conditions they emit with very long lifetimes. The extremely long emission lifetimes (e.g., tau = 1.1 ms for [Ru(SnPh3)2(CO)2(dmb)]) are about a thousand times longer than those of the 3MLCT states of the [Ru(Cl)(Me)(CO)2(alpha-diimine)] complexes. This is due to the weak distortion of the former complexes in their 3SBLCT states as seen from the very small Stokes shifts. Remarkably, replacement of Ru by Os hardly influences the absorption and emission energies of these complexes; yet the emission lifetime is shortened because of an increase of spin-orbit coupling. The quantum yield of emission at 80 K is 1-5% for these complexes, which is lower than might be expected on the basis of their slow nonradiative decay.