MLCT Excited State Research Articles

Ru(bpy)3]2+ as a reference in transient absorption spectroscopy: differential absorption coefficients for formation of the long-lived 3MLCT excited state

Transient absorption spectroscopy and other time-resolved methods are commonly used to study chemical reactions and biological processes induced by absorption of light. In order to scale the signal amplitude or to compare results obtained under different conditions, it is advisable to use a reference system, a standard of convenient and well-defined properties. Finding Tris(bipyridine)ruthenium(ii), [Ru(bpy)(3)](2+), a suitable candidate for a transient-absorption spectroscopy reference due to its favourable photochemical properties, we have determined accurate relative values of differential molar absorption coefficients (Δε) for light-induced formation of the metal-to-ligand charge transfer (MLCT) excited triplet state at several relevant wavelengths (wavelengths of commercially available lasers) in the UV and visible regions. We have also attempted to determine the absolute value of Δε close to the wavelength of maximum bleaching (∼450 nm) and we propose to narrow down the interval of conceivable values for Δε(450) from the broad range of published values (-0.88 × 10(4) M(-1)cm(-1) to -1.36 × 10(4) M(-1)cm(-1)) to -1.1 × 10(4) M(-1)cm(-1)± 15%. Having ourselves successfully applied [Ru(bpy)(3)](2+) as a standard in a recent time-resolved study of enzymatic DNA repair, we would like to encourage other scientists to use this convenient tool as a reference in their future spectroscopic studies on time scales from picoseconds to hundreds of nanoseconds.

Ruthenium-Phenothiazine Electron Transfer Dyad with a Photoswitchable Dithienylethene Bridge: Flash-Quench Studies with Methylviologen

A molecular ensemble composed of a phenothiazine (PTZ) electron donor, a photoisomerizable dithienylethene (DTE) bridge, and a Ru(bpy)(3)(2+) (bpy = 2,2'-bipyridine) electron acceptor was synthesized and investigated by optical spectroscopic and electrochemical means. Our initial intention was to perform flash-quench transient absorption studies in which the Ru(bpy)(3)(2+) unit is excited selectively ("flash") and its (3)MLCT excited state is quenched oxidatively ("quench") by excess methylviologen prior to intramolecular electron transfer from phenothiazine to Ru(III) across the dithienylethene bridge. However, after selective Ru(bpy)(3)(2+1)MLCT excitation of the dyad with the DTE bridge in its open form, (1)MLCT → (3)MLCT intersystem crossing on the metal complex is followed by triplet-triplet energy transfer to a (3)π-π* state localized on the DTE unit. This energy transfer process is faster than bimolecular oxidative quenching with methylviologen at the ruthenium site (Ru(III) is not observed); only the triplet-excited DTE then undergoes rapid (10 ns, instrumentally limited) bimolecular electron transfer with methylviologen. Subsequently, there is intramolecular electron transfer with PTZ. The time constant for formation of the phenothiazine radical cation via intramolecular electron transfer occurring over two p-xylene units is 41 ns. When the DTE bridge is photoisomerized to the closed form, PTZ(+) cannot be observed any more. Irrespective of the wavelength at which the closed isomer is irradiated, most of the excitation energy appears to be funneled rapidly into a DTE-localized singlet excited state from which photoisomerization to the open form occurs within picoseconds.

Dual Emission from Rhenium(I) Complexes Induced by an Interligand Aromatic Interaction

A series of rhenium(I) diimine complexes cis,trans-[Re(dmb)(CO)(2)(PR(1)R(2)R(3))(PR(4)R(5)R(6))](+) (dmb=4,4'-dimethyl-2,2'-bipyridine, R(n)=phenyl or alkyl), each of which bears two phosphine ligands with various numbers of phenyl groups, has been synthesized by using the photochemical ligand-substitution reaction. Detailed studies of the structural features, not only in the crystal but also in solution, indicate that the number of phenyl groups is a crucial factor in controlling the rotational conformation of the phosphine ligands, which in turn determines the extent of the π-π interaction between the aromatic diimine ligand and the phenyl group(s). The π-π interaction strongly affected both electrochemical and photophysical properties: 1) the oxidation power of the Re complex became stronger, 2) the lifetime of the excited state became longer, and 3) the Stokes shift between the (1) MLCT absorption band and emission from the corresponding (3) MLCT excited state became smaller. In particular, the diphenyl and triphenyl phosphine had much greater influence on the properties than the monophenyl phosphine ligand. Dual emission was observed from the different rotational conformers of the complexes with an intermediate number of phenyl groups in the phosphine ligands.

Probing Charge-Transfer Excited States in a Quasi-Nonluminescent Electron-Rich Fe(II)–Acetylide Complex by Femtosecond Optical Spectroscopy

Molecules with photoswitchable nonlinear optical (NLO) properties on the nanosecond time scale are attracting considerable attention as potential solid-state components of photonic devices, downsizeable at will, for ultrafast information encoding. In this context, we present here the study of an electron-rich Fe(II) 4-nitrophenylalkynyl complex which possesses a high hyperpolarizability in its singlet ground state and a negative (and presumably much decreased) NLO activity in its first excited MLCT state(s). On the basis of an ensemble of spectroscopic and time-resolved measurements we investigate the ultrafast dynamics for deactivation of the initially populated MLCT singlet state(s) of this particular organometallic complex, which are shown to decay into a metastable triplet state. The purported mechanism is rationalized with DFT calculations. We show that this triplet state, which should also exhibit a strongly diminished hyperpolarizability, is fully formed with a very high quantum yield within 15 ps.

Influence of Triplet State Multidimensionality on Excited State Lifetimes of Bis-tridentate RuII Complexes: A Computational Study

Calculated triplet excited state potential energy surfaces are presented for a set of three bis-tridentate Ru(II)-polypyridyl dyes covering a wide range of room temperature excited state lifetimes: [Ru(II)(tpy)(2)](2+), 250 ps; [Ru(II)(bmp)(2)](2+), 15 ns; and [Ru(II)(dqp)(2)](2+), 3 μs (tpy is 2,2':6',2″-terpyridine, bmp is 6-(2-picolyl)-2,2'-bipyridine, and dqp is 2,6-di(quinolin-8-yl)pyridine). The computational results provide a multidimensional view of the (3)MLCT-(3)MC transition for the investigated complexes. Recently reported results of significantly prolonged (3)MLCT excited state lifetimes of bis-tridentate Ru(II)-complexes, for example [Ru(II)(dqp)(2)](2+), are found to correlate with substantial differences in their triplet excited state multidimensional potential energy surfaces. In addition to identification of low-energy transition paths for (3)MLCT-(3)MC conversion associated with simultaneous elongation of two or more Ru-N bonds for all investigated complexes, the calculations also suggest significant differences in (3)MLCT state volume in the multidimensional reaction coordinate space formed from various combinations of Ru-N bond distance variations. This is proposed to be an important aspect for understanding the large differences in experimentally observed (3)MLCT excited state lifetimes. The results demonstrate the advantage of considering multidimensional potential energy surfaces beyond the Franck-Condon region in order to predict photophysical and photochemical properties of bis-tridentate Ru(II)-polypyridyl dyes and related metal complexes.

Solvent-dependent modulation of metal–metal electronic interactions in a dinuclear cyanoruthenate complex: a detailed electrochemical, spectroscopic and computational study

The dinuclear complex [{Ru(CN)(4)}(2)(μ-bppz)](4-) shows a strongly solvent-dependent metal-metal electronic interaction which allows the mixed-valence state to be switched from class 2 to class 3 by changing solvent from water to CH(2)Cl(2). In CH(2)Cl(2) the separation between the successive Ru(II)/Ru(III) redox couples is 350 mV and the IVCT band (from the UV/Vis/NIR spectroelectrochemistry) is characteristic of a borderline class II/III or class III mixed valence state. In water, the redox separation is only 110 mV and the much broader IVCT transition is characteristic of a class II mixed-valence state. This is consistent with the observation that raising and lowering the energy of the d(π) orbitals in CH(2)Cl(2) or water, respectively, will decrease or increase the energy gap to the LUMO of the bppz bridging ligand, which provides the delocalisation pathway via electron-transfer. IR spectroelectrochemistry could only be carried out successfully in CH(2)Cl(2) and revealed class III mixed-valence behaviour on the fast IR timescale. In contrast to this, time-resolved IR spectroscopy showed that the MLCT excited state, which is formulated as Ru(III)(bppz(˙-))Ru(II) and can therefore be considered as a mixed-valence Ru(II)/Ru(III) complex with an intermediate bridging radical anion ligand, is localised on the IR timescale with spectroscopically distinct Ru(II) and Ru(III) termini. This is because the necessary electron-transfer via the bppz ligand is more difficult because of the additional electron on bppz(˙-) which raises the orbital through which electron exchange occurs in energy. DFT calculations reproduce the electronic spectra of the complex in all three Ru(II)/Ru(II), Ru(II)/Ru(III) and Ru(III)/Ru(III) calculations in both water and CH(2)Cl(2) well as long as an explicit allowance is made for the presence of water molecules hydrogen-bonded to the cyanides in the model used. They also reproduce the excited-state IR spectra of both [Ru(CN)(4)(μ-bppz)](2-) and [{Ru(CN)(4)}(2)(μ-bppz)](4-) very well in both solvents. The reorganization of the water solvent shell indicates a possible dynamical reason for the longer life time of the triplet state in water compared to CH(2)Cl(2).

Metal to ligand charge transfer induced DNA photobinding in a Ru(ii)–Pt(ii) supramolecule using red light in the therapeutic window: a new mechanism for DNA modification

The Ru(II)-Pt(II) supramolecular complex, [(Ph(2)phen)(2)Ru(dpp)PtCl(2)](2+), displays a new mechanism for DNA modification: photobinding through a (3)MLCT excited state. Gel shift analysis, selective DNA precipitation, and DNA melting point experiments support efficient covalent DNA binding following visible light excitation.

A Series of Supramolecular Complexes for Solar Energy Conversion via Water Reduction to Produce Hydrogen: An Excited State Kinetic Analysis of Ru(II),Rh(III),Ru(II) Photoinitiated Electron Collectors.

Mixed-metal supramolecular complexes have been designed that photochemically absorb solar light, undergo photoinitiated electron collection and reduce water to produce hydrogen fuel using low energy visible light. This manuscript describes these systems with an analysis of the photophysics of a series of six supramolecular complexes, [{(TL)2Ru(dpp)}2RhX2](PF6)5 with TL = bpy, phen or Ph2phen with X = Cl or Br. The process of light conversion to a fuel requires a system to perform a number of complicated steps including the absorption of light, the generation of charge separation on a molecular level, the reduction by one and then two electrons and the interaction with the water substrate to produce hydrogen. The manuscript explores the rate of intramolecular electron transfer, rate of quenching of the supramolecules by the DMA electron donor, rate of reduction of the complex by DMA from the 3MLCT excited state, as well as overall rate of reduction of the complex via visible light excitation. Probing a series of complexes in detail exploring the variation of rates of important reactions as a function of sub-unit modification provides insight into the role of each process in the overall efficiency of water reduction to produce hydrogen. The kinetic analysis shows that the complexes display different rates of excited state reactions that vary with TL and halide. The role of the MLCT excited state is elucidated by this kinetic study which shows that the 3MLCT state and not the 3MMCT is likely that key contributor to the photoreduction of these complexes. The kinetic analysis of the excited state dynamics and reactions of the complexes are important as this class of supramolecules behaves as photoinitiated electron collectors and photocatalysts for the reduction of water to hydrogen.

“Click” Synthesis of Heteroleptic Tris-Cyclometalated Iridium(III) Complexes: Cu(I) Triazolide Intermediates as Transmetalating Reagents

Efficient synthesis of heteroleptic tris-cyclometalated Ir(III) complexes mer-Ir(C(/\)N)(2)(trpy) (trpy = 2-(1H-[1,2,3]triazol-4-yl)pyridine) is achieved by using the Cu(I)-triazolide intermediates formed in "click" reactions as transmetalating reagents. Ligand preparation and cyclometalation of Ir(III) is accomplished in one pot. The robust nature of click chemistry provides opportunities to introduce different functional groups to the cyclometalated system, for example, alkyl, perfluoroalkyl, and aryl moieties. All of the meridional isomers show short-lived phosphorescence at room temperature, both in solution and in the solid state. DFT calculations indicates that the phosphorescence of mer-Ir(C(/\)N)(2)(trpy) is attributed to the (3)MLCT and (3)LC mixed excited states, also supported by the broad spectral shape and hypsochromic shift upon media rigidification. The luminescence efficiency and excited state lifetimes of the cyclometalated complexes can be tuned by varying the substituents on the triazole ring, while the emission color is mainly determined by the phenylpyridine-based ligands. Moreover, the trpy ligand can acquire the N(/\)N chelating mode under selective reaction conditions. mer-Ir(C(/\)N)(2)(trpy) complexes isomerize into cationic [Ir(C(/\)N)(2)(N(/\)N_trpy)](+) species instead of their fac isomers upon heating or UV radiation. This can be explained by the strong trans influence exerted by the phenyl groups. The weakened Ir-C(trpy) bonds are likely to be activated and protonated, leading to the switch of the trpy ligand to a thermodynamically more stable N(/\)N chelating mode.

Photoinduced Intramolecular Tryptophan Oxidation and Excited-State Behavior of [Re(L-AA)(CO)3(α-diimine)]+ (L = Pyridine or Imidazole, AA = Tryptophan, Tyrosine, Phenylalanine)

Re(I) carbonyl-diimine complexes [Re(L-AA)(CO)(3)(N,N)](+) (N,N = bpy, phen) containing an aromatic amino acid (AA), phenylalanine (Phe), tyrosine (Tyr), or tryptophan (Trp), linked to Re by a pyridine-amido or imidazole-amido ligand L have been synthesized and their excited-state properties investigated by nanosecond time-resolved IR (TRIR) and emission spectroscopy. Near-UV optical excitation populates a Re(I)(CO)(3)→N,N (3)MLCT excited state *[Re(II)(L-AA)(CO)(3)(N,N(•-))](+). Decay to the ground state (50-300 ns lifetime) is the only excited-state deactivation process observed in the case of Phe and Tyr complexes, whereas the Trp-containing species undergo a Trp(indole)→*Re(II) electron transfer (ET) producing a charge-separated (CS) state, [Re(I)(L-Trp(•+))(CO)(3)(N,N(•-))](+). The ET occurs with a 8-40 ns lifetime depending on L, N,N, and the solvent. The CS state is characterized by ν(CO) IR bands shifted to lower wavenumbers from their respective ground-state positions and two bands at 1278 and 1497 cm(-1) tentatively attributed to Trp(•+). The amido bridge is affected by both the MLCT excitation and the subsequent ET, manifested by the shifts and intensity changes of the amide-I IR band at about 1680 cm(-1). The CS state decays to the ground state by a N,N(•-)→Trp(•+) back-ET the rates of which are comparable to those of the forward ET, 30-60 ns. This study independently demonstrates that Trp can act as an electron-hopping intermediate in photodriven ET systems based on Re-labeled proteins and supramolecules. Photoinduced ET in Trp-containing Re complexes also can be used to generate Trp(•+) and investigate its spectral properties and reactivity.

Evidence for Strong Mixing Between the LC and MLCT Excited States in Some Heteroleptic Iridium (III) Complexes

The synthesis, structure and photophysical properties of series of new luminescent cyclometalated Iridium (III) complexes are reported. The cyclometalated ligand used here is 2-aryl imidazole and the auxiliary ligand is acetyl acetone (acac). The crystal structure of the complex (dmdpi)(2)Ir(acac) (5) show that the Iridium(III) ion resides in a distorted octahedral environment. All complexes exhibit bright photoluminescence (PL) at room temperature and (fpdmdmpi)(2)Ir(acac) 4 has a high solution PL quantum efficiency of 0.56. The role played by electron releasing and electron withdrawing substituents of the 2-arylimidazole ligands towards the stability of HOMO and how the substituent influences the luminescent behaviour are discussed. Furthermore those substituents have effect on the contribution to mixing between (3)(π-π*) and (3)(MLCT) for the lowest excited states.

Sensitization of TiO2 by the MLCT Excited State of CoI Coordination Compounds

CoI coordination compounds, based on porphyrin or glyoxime ligands, anchored to TiO2 nanocrystallites interconnected in a mesoporous thin film were found to efficiently inject electrons into TiO2 when excited with visible or near-infrared light. When a cobalt metalloporphyrin sensitizer was employed, electron injection was rapid and led to a long-lived (millisecond time scale) charge-separated state whose recombination kinetics were nonexponential but were first order in the concentration of TiO2 electrons. The MLCT excited state was found to inject electrons more efficiently than the π → π* excited state of the porphyrin, even though unfilled d orbitals were present. These findings provide an earth-abundant metal to use in coordination compounds for sensitization of wide-band-gap semiconductor nanoparticles, especially those whose conduction band edges are generally closer to the vacuum level.

Synthesis, structure, photophysical and electrochemiluminescence properties of Re(i) tricarbonyl complexes incorporating pyrazolyl–pyridyl-based ligands

Three rhenium carbonyl complexes 1-3 were synthesized by reaction of the appropriate bidentate pyrazolyl-pyridyl-based ligand L1, L2 (L1 = 2-[1-{4-(bromomethyl)benzyl}-1H-pyrazol-3-yl]pyridine; L2 = 1,4-bis(3-(2-pyridyl)pyrazol-1-ylmethyl)benzene) with [Re(CO)(5)Cl] in toluene. They were characterized by elemental analyses, ESI-MS, (1)H spectroscopy, and X-ray crystallography for 1 and 2. Compounds 1-3 exhibit bright yellow-green luminescence in the solid state and in solution at 298 K with the lifetimes in the microsecond range. It is noteworthy that the luminescent quantum efficiencies of compounds 1-3 are between 0.040 and 0.051, which are much higher than that of the [Re(bpy)(CO)(3)Cl] complex (= 0.019) (M. M. Richter et al., Anal. Chem., 1996, 68, 4370; J. Van Houten et al., J. Am. Chem. Soc., 1976, 98, 4853). Electrogenerated chemiluminescence (ECL) was observed in solutions of these complexes in the absence or presence of coreactant tri-n-propylamine (TPrA) or 2-(dibutylamino)ethanol (DBAE) by stepping the potential of a Pt disk working electrode. The ECL spectra are identical to the photoluminescence spectra, indicating that the chemical reactions following electrochemical oxidation or reduction form the same (3)MLCT excited states as that generated in the photoluminescence experiments. In most cases, the ECL quantum efficiencies of complexes 1-3 are comparable to that of the [Re(L)(CO)(3)Cl] (L = bpy or phen) system. Oxygen tends to substantially decrease ECL intensities of the three rhenium complexes-TPrA system, which could allow them to be used as oxygen sensors.

Influence of the Fluid-to-Film Transition on Photophysical Properties of MLCT Excited States in a Polymerizable Dimethacrylate Fluid

Photophysical properties of the salts [Ru(bpy)(3)](p-Tos)(2), [Ru(dmb)(3)](PF(6))(2), [Ru(vbpy)(3)](PF(6))(2), and [Ru(phen)(3)](p-Tos)(2) (bpy = 2,2'-bipyridine, dmb = 4,4'-dimethyl-2,2'-bipyridine, vbpy = 4-methyl-4'-vinyl-2,2'-bipyridine, phen = 1,10-phenanthroline, and p-Tos = p-toluene sulfonate) in fluid and film polyethylene glycol dimethacrylate containing nine ethylene glycol spacers (PEG-DMA550) are reported. MLCT absorption energies and bandshapes are similar in fluid and film PEG-DMA550 pointing to similar local dielectric environments, presumably dominated by the polar acrylate groups. Emission energies and excited-to-ground state 0-0 energy gaps (E(0)), determined by emission spectral fitting, are blue-shifted, and band-widths-at-half height (Δv(0,1/2)) decreased, due to an expected "rigid medium effect" in PEG-DMA550 film. The extent of loss of medium dipole reorientation in the rigid environment, and the increased emission energies in the film, resulted in enhanced emission quantum yields and excited state lifetimes in accordance with the energy gap law. The "rigid medium effect" in PEG-DMA550 is less pronounced than in films of poly(methyl methacrylate) (PMMA) pointing to a more fluid-like local environment presumably arising from the ethylene glycol linker spacers in PEG-DMA550. Comparison of the absorption, emission, emission spectral fitting, and emission lifetime results for [Ru(dmb)(3)](PF(6))(2) and [Ru(vbpy)(3)](PF(6))(2) shows that the vinyl groups of vbpy copolymerize with PEG-DMA550 covalently incorporating Ru(vbpy)(3)(2+) as a cross-linker into the polymer network. The most dramatic effect of the fluid-to-film transition is seen in the emission lifetime data for [Ru(phen)(3)](p-Tos)(2), with an increase of ~3 in the PEG-DMA550 film. Ru(phen)(3)(2+) cations appear to occupy a low symmetry site in the films probably close to the polar acrylate groups in a structurally confined environment.

A Structurally Diverse RuII,PtII Tetrametallic Motif for Photoinitiated Electron Collection and Photocatalytic Hydrogen Production

Coupling a reactive metal to light absorbers affords molecular devices for photoinitiated electron collection and photocatalytic conversion of substrates to fuels. A new Ru(II),Pt(II) tetrametallic supramolecule, [{(phen)(2)Ru(dpp)}(2)Ru(dpq)PtCl(2)](PF(6))(6), and the trimetallic precursors, [{(phen)(2)Ru(dpp)}(2)RuCl(2)](PF(6))(4) and [{(phen)(2)Ru(dpp)}(2)Ru(dpq)](PF(6))(6), have been synthesized, and their redox, spectroscopic, spectroelectrochemical, photophysical and photocatalytic properties studied. They efficiently absorb UV and visible light. The electrochemistry of [{(phen)(2)Ru(dpp)}(2)Ru(dpq)PtCl(2)](PF(6))(6) suggests a lowest-lying terminal Ru→dpq charge-separated state that quenches the emission of the parent complex with non-unity population of the emissive (3)MLCT excited state. Photolysis of [{(phen)(2)Ru(dpp)}(2)Ru(dpq)PtCl(2)](6+) at 470 nm with DMA gives multielectron reduction, storing electrons in a new manner on the central (dpp)(2)Ru(II)(dpq) moiety. Addition of H(2)O to the photolysis system produces 21 μmol of H(2) in 5 h, with 115 turnovers of the tetrametallic photocatalyst.

Effect of intraligand π-delocalization on the photophysical properties of two new Ru(II) complexes

Two new Ru(II) complexes, [Ru(bpy) 2(1-COO-iqu)] + ( 2; bpy = 2,2′-bipyridine, 1-COO-iqu − = isoquinoline-1-carboxylate) and [Ru(bpy) 2(3-COO-iqu)] + ( 3; 3-COO-iqu − = isoquinoline-3-carboxylate), were prepared and their crystal structures solved. The ground and excited state properties of 2 and 3 were characterized and compared to those of [Ru(bpy) 3] 2+ ( 1). The presence of the oxygen atom in the Ru(II) coordination sphere makes 2 and 3 easier to oxidize than 1. The Ru → bpy MLCT absorption and emission of 2 and 3 are red-shifted relative to that of 1 in CH 2Cl 2, and the E 00 energies were estimated to be 1.89 eV and 1.95 eV from the low temperature emission of 2 and 3, resulting in excited state oxidation potentials of −1.03 V and −1.10 V vs SCE, respectively. In addition to the short-lived emissive 3MLCT state, a long-lived species is observed in the transient absorption of 3 in DMSO ( τ = 49 μs) and pyridine ( τ = 44 μs), assigned to a solvent-coordinated complex. This intermediate is not observed for 3 in non-polar solvents or for 2. The absence of the solvent coordinated intermediate in 2 is explained by the stronger Ru–O bond afforded by the lower conjugation in that extends onto the carboxylic acid in the 1-COO-iquo −ligand, compared to that in the 3-COO-iqu −ligand in 3. Transient absorption experiments also show that the 3MLCT excited state of 3 is able to reduce methyl viologen.

ChemInform Abstract: A Room Temperature Luminescent Cyclometallated Ruthenium(II) Complex of 6-Phenyl-2,2′-bipyridine.

Abstract The cyclometallated complex Ru(tt)(phbp) + (tt=4′-tolyl-2,2′:6′2″-terpyridine, phbp=6-phenyl-2,2′-bipyridine) with a (N,N,N)(C,N,N) coordination, has been synthesized and characterized by 1 H NMR, UV, FAB-MS spectral techniques and by elemental analysis. We have compared its electrochemical and photophysical properties with those of the non-orthometallated analogues Ru(tt) 2 2+ and Ru(terpy) 2 2+ (terpy=2,2′:6′,2″-terpyridine). The most remarkable feature of Ru(tt)(phbp) + is its ability to luminesce at room temperature in alcoholic and nitrile solvents. The lifetime of its 3 MLCT excited state is 60 ns in CH 3 CN.

Emission Spectroscopy as a Probe into Photoinduced Intramolecular Electron Transfer in Polyazine Bridged Ru(II),Rh(III) Supramolecular Complexes.

Steady-state and time-resolved emission spectroscopy are valuable tools to probe photochemical processes of metal-ligand, coordination complexes. Ru(II) polyazine light absorbers are efficient light harvesters absorbing in the UV and visible with emissive 3MLCT excited states known to undergo excited state energy and electron transfer. Changes in emission intensity, energy or band-shape, as well as excited state lifetime, provide insight into excited state dynamics. Photophysical processes such as intramolecular electron transfer between electron donor and electron acceptor sub-units may be investigated using these methods. This review investigates the use of steady-state and time-resolved emission spectroscopy to measure excited state intramolecular electron transfer in polyazine bridged Ru(II),Rh(III) supramolecular complexes. Intramolecular electron transfer in these systems provides for conversion of the emissive 3MLCT (metal-to-ligand charge transfer) excited state to a non-emissive, but potentially photoreactive, 3MMCT (metal-to-metal charge transfer) excited state. The details of the photophysics of Ru(II),Rh(III) and Ru(II),Rh(III),Ru(II) systems as probed by steady-state and time-resolved emission spectroscopy will be highlighted.

Syntheses, Characterization, and Photo-Hydrogen-Evolving Properties of Tris(2,2'-bipyridine)ruthenium(II) Derivatives Tethered to an H2-Evolving (2-phenylpyridinato)platinum(II) Unit

With the aim of developing new molecular devices having higher photo-hydrogen-evolving activity, Pt(ppy)ClX units (ppy = 2-phenylpyridinate, X = Cl- or DMSO; DMSO = dimethylsulfoxide) have been employed as an H2-evolving site, as the catalytic activity of [Pt(ppy)Cl2]- was confirmed to be higher than those of other mononuclear platinum(II) complexes. In the present study, two new heterodinuclear Ru(II)Pt(II) complexes, produced by condensation of [Ru(bpy)2(5-amino-phen)]2+ (bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline) with [Pt(cppy)Cl2]- and Pt(cppy)(DMSO)Cl (cppy = 9-carboxy-phenylpyridinate), respectively, have been prepared and their photo-hydrogen-evolving activities have been evaluated in detail. The ineffectiveness of these systems as photo-hydrogen-evolving molecular devices are interpreted in terms of their negative driving forces for the photoinduced electron transfer from the triplet MLCT excited state of the Ru chromophore to the π*(ppy) orbital of the catalyst moiety.

Excited State Absorption Properties of Pt(II) Terpyridyl Complexes Bearing π-Conjugated Arylacetylides

The synthesis, photophysics, and excited state absorption properties of three platinum(II) terpyridyl acetylide charge transfer (CT) complexes possessing a lone ancillary ligand systematically varied in phenylacetylide (PA) π-conjugation length, [Pt((t)Bu(3)tpy)([C≡C-C(6)H(4)](n)-H)]ClO(4) (n = 1, 2, 3), are described. Density functional theory (DFT) calculations performed on the ground states of complexes 1, 2, and 3 reveal that their HOMOs reside mainly on the ancillary π-conjugated PA moiety, ranging from 86 to 97%, with LUMOs predominantly centered on the terpyridyl acceptor ligand (91-92%). This electronic structure leads to the production of a triplet ligand-to-ligand CT ((3)LLCT) excited state upon visible light excitation with minor contributions from the corresponding triplet metal-to-ligand CT ((3)MLCT) excited state. Unusually strong red-to-near-IR transient absorptions are produced in the excited states of these molecules following selective long wavelength visible excitation of the low energy CT bands that do not emanate from the terpyridyl radical anion produced in the CT excited state or from an arylacetylide-based triplet intraligand ((3)IL) excited state. The extinction coefficients of these low energy absorption transients were determined using the energy transfer method with anthracene serving as the triplet acceptor. A detailed theoretical investigation using DFT and TDDFT methods reveals that these intense near-IR transient absorptions involve transitions resulting from transient oxidation of the PA subunit. In essence, the production of the (3)LLCT excited state transiently oxidizes the PA moiety by one electron, producing the corresponding highly absorbing radical cation-like species, analogous to that experienced in related intramolecular photoinduced electron transfer reactions. The computational work successfully predicts the oscillator strength and peak wavelength of the measured excited state absorption transients across this series of molecules. In the present effort, there is a convergence of theory and experiment given that the excited state absorption properties of these Pt(II) chromophores are determined by localized transitions that resemble open shell radical cation species.