Static and dynamic quenching of Ru(II) polypyridyl excited states by iodide

The metal-to-ligand charge-transfer (MLCT) excited states of Ru(bpy)(2)(deeb)(PF(6))(2), where bpy is 2,2-bipyridine and deeb is 4,4'-(CO(2)CH(2)CH(3))(2)-2,2'-bipyridine, in dichloromethane were found to be efficiently quenched by iodide at room temperature. The ionic strength dependence of the UV-visible absorption spectra gave evidence for ion pairing. Iodide was found to quench the excited states by static and dynamic mechanisms. Stern-Volmer and Benesi-Hildebrand analysis of the spectral data provided a self-consistent estimate of the iodide-Ru(bpy)(2)(deeb)(2+) adduct in dichloromethane, K = 59 700 M(-1). Transient absorption studies clearly demonstrated an electron-transfer quenching mechanism with transient formation of I(2)(*)(-) in high yield, phi = 0.25 for 355 or 532 nm excitation. For Ru(bpy)(2)(deeb)(PF(6))(2) in acetonitrile, similar behavior could be observed at higher iodide concentrations than that required in dichloromethane. The parent Ru(bpy)(3)(2+) compound also ion pairs with iodide in CH(2)Cl(2), and light excitation gave a higher I(2)(*)(-) yield, phi = 0.50. X-ray crystallographic, IR, and Raman data gave evidence for interactions between iodide and the coordinated deeb ligand in the solid state.     

Triiodide quenching of ruthenium MLCT excited state in solution and on TiO2 surfaces: an alternate pathway for charge recombination

The excited states of [Ru(bpy)2(deeb)](PF6)2, where bpy is 2,2-bipyridine and deeb is 4,4'-(CO2CH2CH3)2-2,2'-bipyridine, were found to be efficiently quenched by triiodide (I3-) in acetonitrile and dichloromethane. In dichloromethane, I3- was found to quench the excited states by static and dynamic mechanisms; Stern-Volmer analysis of the time-resolved and steady-state photoluminescence data produced self-consistent estimates for the I3- + Ru(bpy)2(deeb)2+ <==> [Ru(II)(bpy)2(deeb)2+,(I3-)]+ equilibrium, K = 51,000 M(-1), and the bimolecular quenching rate constant, kq = 4.0 x 10(10) M(-1) s(-1). In acetonitrile, there was no evidence for ion pairing and a dynamic quenching rate constant of k(q) = 4.7 x 10(10) M(-1) s(-1) was calculated. Comparative studies with Ru(bpy)2(deeb)2+ anchored to mesoporous nanocrystalline TiO2 thin films also showed efficient excited-state dynamic quenching by I3- in both acetonitrile and dichloromethane, kq = 1.8 x 10(9) and 3.6 x 10(10) M(-1) s(-1), respectively. No reaction products for the excited-state quenching processes were observed by nanosecond transient absorption measurements from 350 to 800 nm under any experimental conditions. X-ray crystallographic, IR, and Raman data gave evidence for interactions between I3- and the bpy and deeb ligands in the solid state.     

Influence of ion pairing on the oxidation of iodide by MLCT excited states

The oxidation of iodide to diiodide, I(2)˙(-), by the metal-to-ligand charge-transfer (MLCT) excited state of [Ru(deeb)(3)](2+), where deeb is 4,4'-(CO(2)CH(2)CH(3))(2)-2,2'-bipyridine, was quantified in acetonitrile and dichloromethane solution at room temperature. The redox and excited state properties of [Ru(deeb)(3)](2+) were similar in the two solvents; however, the mechanisms for excited state quenching by iodide were found to differ significantly. In acetonitrile, reaction of [Ru(deeb)(3)](2+*) and iodide was dynamic (lifetime quenching) with kinetics that followed the Stern-Volmer model (K(D) = 1.0 ± 0.01 × 10(5) M(-1), k(q) = 4.8 × 10(10) M(-1) s(-1)). Excited state reactivity was observed to be the result of reductive quenching that yielded the reduced ruthenium compound, [Ru(deeb(-))(deeb)(2)](+), and the iodine atom, I˙. In dichloromethane, excited state quenching was primarily static (photoluminescence amplitude quenching) and [Ru(deeb(-))(deeb)(2)](+) formed within 10 ns, consistent with the formation of ion pairs in the ground state that react rapidly upon visible light absorption. In both solvents the appearance of I(2)˙(-) could be time resolved. In acetonitrile, the rate constant for I(2)˙(-) growth, 2.2 ± 0.2 × 10(10) M(-1) s(-1), was found to be about a factor of two slower than the formation of [Ru(deeb(-))(deeb)(2)](+), indicating it was a secondary photoproduct. The delayed appearance of I(2)˙(-) was attributed to the reaction of iodine atoms with iodide. In dichloromethane, the growth of I(2)˙(-), 1.3 ± 0.4 × 10(10) M(-1) s(-1), was similar to that in acetonitrile, yet resulted from iodine atoms formed within the laser pulse. These results are discussed within the context of solar energy conversion by dye-sensitized solar cells and storage via chemical bond formation.     

Intermolecular energy transfer across nanocrystalline semiconductor surfaces

The yields and dynamics for energy transfer from the metal-to-ligand charge-transfer excited states of Ru(deeb)(bpy)(2)(PF(6))(2), Ru(2+), and Os(deeb)(bpy)(2)(PF(6))(2), Os(2+), where deeb is 4,4'-(CH(3)CH(2)CO(2))(2)-2,2'-bipyridine, anchored to mesoporous nanocrystalline (anatase) TiO(2) thin films were quantified. Lateral energy transfer from Ru(2+)* to Os(2+) was observed, and the yields were measured as a function of the relative surface coverage and the external solvent environment (CH(3)CN, THF, CCl(4), and hexanes). Excited-state decay of Ru(2+)*/TiO(2) was well described by a parallel first- and second-order kinetic model, whereas Os(2+)*/TiO(2) decayed with first-order kinetics within experimental error. The first-order component was assigned to the radiative and nonradiative decay pathways (tau = 1 micros for Ru(2+)*/TiO(2) and tau = 50 ns for Os(2+)*/TiO(2)). The second-order component was attributed to intermolecular energy transfer followed by triplet-triplet annihilation. An analytical model was derived that allowed determination of the fraction of excited-states that follow the two pathways. The fraction of Ru(2+)*/TiO(2) that decayed through the second-order pathway increased with surface coverage and excitation intensity. Monte Carlo simulations were performed to estimate the Ru(2+)* --> Ru(2+) intermolecular energy transfer rate constant of (30 ns)(-1).     

A nuclear isotope effect for interfacial electron transfer: excited-state electron injection from Ru ammine compounds to nanocrystalline TiO2

The coordination compounds Ru(deeb)(NH3)4(PF6)2 and Ru(deeb)(NH2(CH2)2NH2)4(PF6)2, where deeb is 4,4'-(CO2CH2CH3)2-2,2'-bipyridine, were synthesized and attached to optically transparent nanocrystalline (anatase) TiO2 films. The compounds were found to be nonemissive in fluid acetonitrile and when attached to TiO2 with excited-state lifetimes <10 ns. Infrared measurements showed the expected isotopic substitution of the deuterated compounds on TiO2 thin films. A small 10-15 mV shift in the RuIII/II reduction potentials was measured upon deuteration. Metal-to-ligand charge-transfer (MLCT) excitation resulted in interfacial electron transfer into the TiO2 semiconductor with quantum yields that were dependent on the excitation wavelength and deuteration of the ammine ligands. The quantum yields were optimized with blue light excitation (417 nm) and deuterium substitution. In contrast, the kinetic rate constants for charge recombination were insensitive to deuteration and the excitation wavelength. Control experiments with Ru(deeb)(bpy)2(PF6)2 indicated that deuteration of the TiO2 surface alone does not affect the injection or recombination processes. A model is proposed wherein electron injection occurs in competition with vibrational relaxation and/or intersystem crossing of the excited states. Exchange of hydrogen by deuterium slows vibrational relaxation and/or intersystem crossing, resulting in higher injection yields.     

Flash-quench technique employed to study the one-electron reduction of triiodide in acetonitrile: evidence for a diiodide reaction product

The one-electron reduction of triiodide (I(3)(-)) by a reduced ruthenium polypyridyl compound was studied in an acetonitrile solution with the flash-quench technique. Reductive quenching of the metal-to-ligand charge-transfer excited state of [Ru(II)(deeb)(3)](2+) by iodide generated the reduced ruthenium compound [Ru(II)(deeb(-))(deeb)(2)](+) and diiodide (I(2)(?-)). The subsequent reaction of [Ru(II)(deeb(-))(deeb)(2)](+) with I(3)(-) indicated that I(2)(?-) was a product that appeared with a second-order rate constant of (5.1 ± 0.2) × 10(9) M(-1) s(-1). After correction for diffusion and some assumptions, Marcus theory predicted a formal potential of -0.58 V (vs SCE) for the one-electron reduction of I(3)(-). The relevance of this reaction to solar energy conversion is discussed.     

Reactions of acetonitrile coordinated to a nitrosylruthenium complex with H2O or CH(3)OH under mild conditions: structural characterization of imido-type complexes

The reaction of cis-[Ru(NO)(CH(3)CN)(bpy)(2)](3+) (bpy = 2,2'-bipyridine) in H(2)O at room temperature proceeded to afford two new nitrosylruthenium complexes. These complexes have been identified as nitrosylruthenium complexes containing the N-bound methylcarboxyimidato ligand, cis-[Ru(NO)(NH=C(O)CH(3))(bpy)(2)](2+), and methylcarboxyimido acid ligand, cis-[Ru(NO)(NH=C(OH)CH(3))(bpy)(2)](3+), formed by an electrophilic reaction at the nitrile carbon of the acetonitrile coordinated to the ruthenium ion. The X-ray structure analysis on a single crystal obtained from CH(3)CN-H(2)O solution of cis-[Ru(NO)(NH=C(O)CH(3))(bpy)(2)](PF(6))(3) has been performed: C(22)H(20.5)N(6)O(2)P(2.5)F(15)Ru, orthorhombic, Pccn, a = 15.966(1) A, b = 31.839(1) A, c = 11.707(1) A, V = 5950.8(4) A(3), and Z = 8. The structural results revealed that the single crystal consisted of 1:1 mixture of cis-[Ru(NO)(NH=C(O)CH(3))(bpy)(2)](2+) and cis-[Ru(NO)(NH=C(OH)CH(3))(bpy)(2)](3+) and the structural formula of this single crystal was thus [Ru(NO)(NH=C(OH(0.5))CH(3))(bpy)(2)](PF(6))(2.5). The reaction of cis-[Ru(NO)(CH(3)CN)(bpy)(2)](3+) in dry CH(3)OH-CH(3)CN at room temperature afforded a nitrosylruthenium complex containing the methyl methylcarboxyimidate ligand, cis-[Ru(NO)(NH=C(OCH(3))CH(3))(bpy)(2)](3+). The structure has been determined by X-ray structure analysis: C(25)H(29)N(8)O(18)Cl(3)Ru, monoclinic, P2(1)/c, a = 13.129(1) A, b = 17.053(1) A, c = 15.711(1) A, beta = 90.876(5) degrees, V = 3517.3(4) A(3), and Z = 4.     

Mono- and dinuclear ruthenium(II) 1,6,7,12-tetraazaperylene complexes

We report the synthesis of free 1,6,7,12-tetraazaperylene (tape). Tape was obtained from 1,1'-bis-2,7-naphthyridine by potassium promoted cyclization followed by oxidation with air. Mono- and dinuclear ruthenium(II) 1,6,7,12-tetraazaperylene complexes of the general formulas [Ru(L-L)(2)(tape)](PF(6))(2), [1](PF(6))(2)-[5](PF(6))(2), and [{Ru(L-L)(2)}(2)(μ-tape)](PF(6))(4), [6](PF(6))(4)-[10](PF(6))(4), with{L-L = phen, bpy, dmbpy (4,4'-dimethyl-2,2'-bipyridine), dtbbpy (4,4'-ditertbutyl-2,2'-bipyridine) and tmbpy (4,4'5,5'-tetramethyl-2,2'-bipyridine)}, respectively, were synthesized. The X-ray structures of tape·2CHCl(3) and the mononuclear complexes [Ru(bpy)(2)(tape)](PF(6))(2)·0.5CH(3)CN·0.5toluene, [Ru(dmbpy)(2)(tape)](PF(6))(2)·2toluene and [Ru(dtbbpy)(2)(tape)](PF(6))(2)·3acetone·0.5H(2)O were solved. The UV-vis absorption spectra and the electrochemical behavior of the ruthenium(ii) tape complexes were explored and compared with the data of the analogous dibenzoeilatin (dbneil), 2,2'-bipyrimidine (bpym) and tetrapyrido[3,2-a:2',3'-c:3',2'-h:2',3'-j]phenazin (tpphz) species.     

High-extinction ruthenium compounds for sunlight harvesting and hole transport

The compounds Ru(bpy) 2(BTL)(PF 6) 2 and Ru(deeb) 2(BTL)(PF 6) 2, where bpy is 2,2'-bipyridine, deeb is 4,4'-(C 2H 5CO 2) 2-bpy, and BTL is 9'-[4,5-bis(cyanoethylthio)]-1,3-dithiol-2-ylidene]-4',5'-diazafluorene, were found to have very high extinction coefficients in the visible region. In an acetonitrile solution, the extinction of Ru(deeb) 2(BTL)(PF 6) 2 was = 44 000 +/- 1000 M (-1) cm (-1) at lambda = 470 nm. Two quasi-reversible oxidation waves, E 1/2 = +0.88 and +1.16 V, and an irreversible reduction, E pr = -1.6 V, were observed versus ferrocene (Fc (+/0)). At -40 degrees C, a state was observed with spectroscopic properties characteristic of a metal-to-ligand charge-transfer excited state, tau = 25 ns. This same compound was found to photoinject electrons into TiO 2 with a quantum yield Phi = 0.3 +/- 0.2 for 532.5 or 417 nm light excitation in a 0.1 M LiClO 4/acetonitrile electrolyte. In regenerative solar cells, a sustained photocurrent was observed with a maximum incident photon-to-current efficiency of 0.4. The photocurrent action and absorptance spectra were in good agreement, consistent with injection from a single excited state.     

Tuning open circuit photovoltages with tripodal sensitizers

The sensitizers [Ru(bpy)2(deeb)](PF6)2 (1), [Ru(bpy)2(bpy)-(E-Ph)-Ad](PF6)2 (2), and [Ru(bpy)2(bpy)-(E-Ph)2-Ad](PF6)2 (3), where deeb is 4,4'-(COOCH2CH3)2-2,2'-bipyridine, E-Ph is phenylethynyl, and Ad are tripod shaped bpy ligands based on 1,3,5,7-tetraphenyladamantane, were anchored to mesoporous nanocrystalline (anatase) TiO2 thin films and studied in regenerative solar cells with 0.1 M LiI/0.005 M I2 dichloromethane electrolyte. Over three decades of 488 nm irradiance, the open circuit photovoltage increased markedly with the distance between the Ru center and the surface binding groups, 1 (7 A) < 2 (18 A) < 3 (24 A). The diode equation accurately models the irradiance dependent data and indicates that the TiO2(e-) --> I3- (and/or I2) charge recombination rate constants were decreased by a factor of 20 for 2/TiO2 and 280 for 3/TiO2 relative to 1/TiO2. The results suggest that control of the sensitizer-TiO2 orientation is important for efficient power optimization.     

Interaction between biimidazole complexes of ruthenium and acetate: hydrogen bonding and proton transfer

The hydrogen bonding and deprotonation processes between four ruthenium biimidazole complexes, namely [Ru(bpy)(2)(BiimH(2))](PF(6))(2) (1, bpy is bipyridine, BiimH(2) is 2,2'-biimidazole), [Ru(bpy)(2)-(BbimH(2))](PF(6))(2) (2, BbimH(2) is 2,2'-bibenzimidazole), and [Ru(bpy)(2)(DMBbimH(2))](PF(6))(2) (3, DMBbimH(2) is 7,7'-dimethyl-2,2'-bibenzimidazole) and [Ru(bpy)(2)(TMBbimH(2))](2+) (4, TMBbimH(2) is 5,6,5',6'-tetramethyl-2,2'-bibenzimidazole), and acetate are investigated. Their hydrogen bonded adducts are indeed trapped and observed by absorption spectra and electrochemical experiments in acetonitrile solution in the presence of an excess of acetic acid for the first time. The binding constants log K(B) for these adducts are 6.74 for 1·OAc, 7.11 for 2·OAc, 7.26 for 3·OAc, and 6.99 for 4·OAc. A new approach to calculate the deprotonation constant is also developed by establishing a set of circular equilibria. The equilibrium constants for the first deprotonation step of the complexes log K(A) are 2.74 for 1, 5.19 for 2, 4.54 for 3, and 3.78 for 4. The pK(a1) values of the complexes in acetonitrile solution are calculated by subtracting log K(A) from pK(a) (HOAc in acetonitrile), giving 19.6 for 1, 17.1 for 2, 17.8 for 3, and 18.5 for 4. The degree of proton transfer (D(PT)) can be quantified by the calculation of absorption spectral and redox data, which is 0.41 for 1·OAc, 0.53 for 2·OAc, 0.57 for 3·OAc, and 0.47 for 4·OAc. Interestingly, the binding constant log K(B) (7.26) and D(PT) value (0.57) both reach their maxima at a critical point, where pK(a1) for the complex is 17.8 and ΔpK(a) for the adduct is 4.5 (ΔpK(a) = pK(a)(HOAc) - pK(a1), in acetonitrile solution). Moreover, the binding constant log K(B) shows linear correlation with the degree of proton transfer D(PT).     

Reversible molecular switching of ruthenium bis(bipyridyl) groups bonded to oligothiophenes: effect on electrochemical and spectroscopic properties

We report the preparation of complexes in which ruthenium(II) bis(bipyridyl) groups are coordinated to oligothiophenes via a diphenylphosphine linker and a thienyl sulfur (P,S bonding) to give [Ru(bpy)(2)PT(3)-P,S](PF(6))(2) (bpy = 2,2'-bipyridyl, PT(3) = 3'-(diphenylphosphino)-2,2':5',2' '-terthiophene), [Ru(bpy)(2)PMeT(3)-P,S](PF(6))(2) (PMeT(3) = 3'-(diphenylphosphino)-5-methyl-2,2':5',2' '-terthiophene), [Ru(bpy)(2)PMe(2)T(3)-P,S](PF(6))(2) (PMe(2)T(3) = 5,5' '-dimethyl-3'-(diphenylphosphino)-2,2':5',2' '-terthiophene), and [Ru(bpy)(2)PDo(2)T(5)-P,S](PF(6))(2) (PDo(2)T(5) = 3,3' ' '-didodecyl-3' '-diphenylphosphino-2,2':5',2' ':5' ',2' ':5' ',2' ' '-pentathiophene). These complexes react with base, resulting in the complexes [Ru(bpy)(2)PT(3)-P,C]PF(6), [Ru(bpy)(2)PMeT(3)-P,C]PF(6), [Ru(bpy)(2)PMe(2)T(3)-P,C]PF(6), and [Ru(bpy)(2)PDo(2)T(5)-P,C]PF(6), where the thienyl carbon is bonded to ruthenium (P,C bonding). The P,C complexes revert back to the P,S bonding mode by reaction with acid; therefore, metal-thienyl bonding is reversibly switchable. The effect of interaction of the metal groups in the different bonding modes with the thienyl backbone is reflected by changes in alignment of the thienyl rings in the solid-state structures of the complexes, the redox potentials, and the pi --> pi transitions in solution. Methyl substituents attached to the terthiophene groups allow observation of the effect of these substituents on the conformational and electronic properties and aid in assignments of the electrochemical data. The PT(n)() ligands bound in P,S and P,C bonding modes also alter the electrochemical and spectroscopic properties of the ruthenium bis(bipyridyl) group. Both bonding modes result in quenching of the oligothiophene luminescence. Weak, short-lived Ru --> bipyridyl MLCT-based luminescence is observed for [Ru(bpy)(2)PDo(2)T(5)-P,S](PF(6))(2), [Ru(bpy)(2)PT(3)-P,C]PF(6), [Ru(bpy)(2)PMeT(3)-P,C]PF(6), and [Ru(bpy)(2)PMe(2)T(3)-P,C]PF(6), and no emission is observed for the alternate bonding mode of each complex.     

Coupling of metal-based light-harvesting antennas and electron-donor subunits: trinuclear ruthenium(II) complexes containing tetrathiafulvalene-substituted polypyridine ligands

Three new tetrathiafulvalene-substituted 2,2'-bipyridine ligands, cis-bpy-TTF(1), trans-bpy-TTF(1), and cis-bpy-TTF(2) have been prepared and characterized. X-ray analysis of trans-bpy-TTF(1) is also reported. Such ligands have been used to prepare two new trinuclear Ru(II) complexes, namely, [[(bpy)(2)Ru(micro-2,3-dpp)](2)Ru(bpy-TTF(1))](PF(6))(6) (9; bpy=2,2'-bipyridine; 2,3-dpp=2,3-bis(2'-pyridyl)pyrazine) and [[(bpy)(2)Ru(micro-2,3-dpp)](2)Ru(bpy-TTF(2))](PF(6))(6) (10). These compounds can be viewed as coupled antennas and charge-separation systems, in which the multichromophoric trinuclear metal subunits act as light-harvesting antennas and the tetrathiafulvalene electron donors can induce charge separation. The absorption spectra, redox behavior, and luminescence properties (both at room temperature in acetonitrile and at 77 K in a rigid matrix of butyronitrile) of the trinuclear metal complexes have been studied. For the sake of completeness, the mononuclear compounds [(bpy)(2)Ru(bpy-TTF(1))](PF(6))(2) (7) and [(bpy)(2)Ru(bpy-TTF(2))](PF(6))(2) (8) were also synthesized and studied. The properties of the tetrathiafulvalene-containing species were compared to those of the model compounds [Ru(bpy)(2)(4,4'-Mebpy)](2+) (4,4'-Mebpy=4,4'-dimethyl-2,2'-bipyridine) and [[(bpy)(2)Ru(micro-2,3-dpp)](2)Ru(bpy)](6+). The absorption spectra and redox behavior of all the new metal compounds can be interpreted by a multicomponent approach, in which specific absorption features and redox processes can be assigned to specific subunits of the structures. The luminescence properties of the complexes in rigid matrices at 77 K are very similar to those of the corresponding model compounds without TTF moieties, whereas the new species are nonluminescent, or exhibit very weak emissions relative to those of the model compounds in fluid solution at room temperature. Time-resolved transient absorption spectroscopy confirmed that the potentially luminescent MLCT states of 7-10 are significantly shorter lived than the corresponding states of the model species. Photoinduced electron-transfer processes from the TTF moieties to the (excited) MLCT chromophore(s) are held responsible for the quenching processes.     

Dye-sensitized SnO2 electrodes with iodide and pseudohalide redox mediators

Dye-sensitized mesoporous nanocrystalline SnO2 electrodes and the pseudohalogen redox mediator (SeCN)2/SeCN- or (SCN)2/SCN- or the halogen redox mediator I3-/I- were implemented for regenerative solar cell studies. Adsorption isotherms of the sensitizers Ru(deeb)(bpy)2(PF6)2, Ru(deeb)2(dpp)(PF6)2, and Ru(deeb2(bpz)(PF6)2, where deeb is 4,4'-diethylester-2,2'-bipyridine, dpp is 2,3-dipyridyl pyrazine, and bpz is bipyrazine, binding to the SnO2 surface were well described by the Langmuir model from which the saturation coverage, Gamma0 = 1.7 x 10(-8) mol/cm2, and surface-adduct formation constant, Kad = 2 x 10(5) M(-1), were obtained. Following excited-state interfacial electron transfer, the oxidized sensitizers were reduced by donors present in the acetonitrile electrolyte as shown by transient absorption spectroscopy. With iodide as the donor, a rate constant k > 10(8) s(-1) was measured for sensitizer regeneration. In regenerative solar cells, it was found that the incident photon-to-current conversion efficiencies and open circuit voltages (Voc) were comparable for (SeCN)2/SeCN- and I3-/I- for all three sensitizers. The Voc varied linearly with the logarithm of the short circuit photocurrent densities (Jsc), with typical correlations of approximately 50-60 mV/decade. Capacitance measurements of the SnO2 electrode in the presence of I3-/I-, (SeCN)2/SeCN- or (SCN)2/SCN- are reported.     

Ruthenium(II)-polyazine light absorbers bridged to reactive cis-dichlororhodium(III) centers in a bimetallic molecular architecture

Bimetallic complexes of the form [(bpy)(2)Ru(BL)RhCl(2)(phen)](PF(6))(3), where bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline, and BL = 2,3-bis(2-pyridyl)pyrazine (dpp) or 2,2'-bipyrimidine (bpm), were synthesized, characterized, and compared to the [{(bpy)(2)Ru(BL)}(2)RhCl(2)](PF(6))(5) trimetallic analogues. The new complexes were synthesized via the building block method, exploiting the known coordination chemistry of Rh(III) polyazine complexes. In contrast to [{(bpy)(2)Ru(dpp)}(2)RhCl(2)](PF(6))(5) and [{(bpy)(2)Ru(bpm)}(2)RhCl(2)](PF(6))(5), [(bpy)(2)Ru(dpp)RhCl(2)(phen)](PF(6))(3) and [(bpy)(2)Ru(bpm)RhCl(2)(phen)](PF(6))(3) have a single visible light absorber subunit coupled to the cis-Rh(III)Cl(2) moiety, an unexplored molecular architecture. The electrochemistry of [(bpy)(2)Ru(dpp)RhCl(2)(phen)](PF(6))(3) showed a reversible oxidation at 1.61 V (vs Ag/AgCl) (Ru(III/II)), quasi-reversible reductions at -0.39 V, -0.74, and -0.98 V. The first two reductive couples corresponded to two electrons, consistent with Rh reduction. The electrochemistry of [(bpy)(2)Ru(bpm)RhCl(2)(phen)](PF(6))(3) exhibited a reversible oxidation at 1.76 V (Ru(III/II)). A reversible reduction at -0.14 V (bpm(0/-)), and quasi-reversible reductions at -0.77 and -0.91 V each corresponded to a one electron process, bpm(0/-), Rh(III/II), and Rh(II/I). The dpp bridged bimetallic and trimetallic display Ru(dpi)-->dpp(pi*) metal-to-ligand charge transfer (MLCT) transitions at 509 nm (14,700 M(-1) cm(-1)) and 518 nm (26,100 M(-1) cm(-1)), respectively. The bpm bridged bimetallic and trimetallic display Ru(dpi)-->bpm(pi*) charge transfer (CT) transitions at 581 nm (4,000 M(-1) cm(-1)) and 594 nm (9,900 M(-1) cm(-1)), respectively. The heteronuclear complexes [(bpy)(2)Ru(dpp)RhCl(2)(phen)](PF(6))(3) and [{(bpy)(2)Ru(dpp)}(2)RhCl(2)](PF(6))(5) had (3)MLCT emissions that are Ru(dpi)-->dpp(pi*) CT in nature but were red-shifted and lower intensity than [(bpy)(2)Ru(dpp)Ru(bpy)(2)](PF(6))(4). The lifetimes of the (3)MLCT state of [(bpy)(2)Ru(dpp)RhCl(2)(phen)](PF(6))(3) at room temperature (30 ns) was shorter than [(bpy)(2)Ru(dpp)Ru(bpy)(2)](PF(6))(4), consistent with favorable electron transfer to Rh(III) to generate a metal-to-metal charge-transfer ((3)MMCT) state. The reported synthetic methods provide means to a new molecular architecture coupling a single Ru light absorber to the Rh(III) center while retaining the interesting cis-Rh(III)Cl(2) moiety.     

New dicarboxylic acid bipyridine ligand for ruthenium polypyridyl sensitization of TiO2

An ambidentate dicarboxylic acid bipyridine ligand, (4,5-diazafluoren-9-ylidene) malonic acid (dfm), was synthesized for coordination to Ru(II) and mesoporous nanocrystalline (anatase) TiO(2) thin films. The dfm ligand provides a conjugated pathway from the pyridyl rings to the carbonyl carbons of the carboxylic acid groups. X-ray crystal structures of [Ru(bpy)(2)(dfm)]Cl(2) and the corresponding diethyl ester compound, [Ru(bpy)(2)(defm)](PF(6))(2), were obtained. The compounds displayed intense metal-to-ligand charge transfer (MLCT) absorption bands in the visible region (ε > 11,000 M(-1) cm(-1) for [Ru(bpy)(2)(dfm)](PF(6))(2) in acetonitrile). Significant room temperature photoluminescence, PL, was absent in CH(3)CN but was observed at 77 K in a 4:1 EtOH:MeOH (v:v) glass. Cyclic voltammetry measurements revealed quasi-reversible Ru(III/II) electrochemistry. Ligand reductions were quasi-reversible for the diethyl ester compound [Ru(bpy)(2)(defm)](2+), but were irreversible for [Ru(bpy)(2)(dfm)](2+). Both compounds were anchored to TiO(2) thin films by overnight reactions in CH(3)CN to yield saturation surface coverages of 3 × 10(-8) mol/cm(2). Attenuated total reflection infrared measurements revealed that the [Ru(bpy)(2)(dfm)](2+) compound was present in the deprotonated carboxylate form when anchored to the TiO(2) surface. The MLCT excited states of both compounds injected electrons into TiO(2) with quantum yields of 0.70 in 0.1 M LiClO(4) CH(3)CN. Micro- to milli-second charge recombination yielded ground state products. In regenerative solar cells with 0.5 M LiI/0.05 M I(2) in CH(3)CN, the Ru(bpy)(2)(dfm)/TiO(2) displayed incident photon-to-current efficiencies of 0.7 at the absorption maximum. Under the same conditions, the diethylester compound was found to rapidly desorb from the TiO(2) surface.     

Luminescent ruthenium(II) polypyridine biotin complexes: synthesis, characterization, photophysical and electrochemical properties, and avidin-binding studies

Two luminescent ruthenium(II) polypyridine complexes containing a biotin moiety [Ru(bpy)(2)(L1)](PF(6))(2) (1) and [Ru(bpy)(2)(L2)](PF(6))(2) (2) (bpy = 2,2'-bipyridine; L1 = 4-(N-((2-biotinamido)ethyl)amido)-4'-methyl-2,2'-bipyridine; L2 = 4-(N-((6-biotinamido)hexyl)amido)-4'-methyl-2,2'-bipyridine) have been synthesized and characterized, and their photophysical and electrochemical properties have been studied. Upon photoexcitation, complexes 1 and 2 display intense and long-lived triplet metal-to-ligand charge-transfer ((3)MLCT) (dpi(Ru) --> pi*(L1 or L2)) emission in fluid solutions at 298 K and in low-temperature glass. We have studied the binding of these ruthenium(II) biotin complexes to avidin by 4'-hydroxyazobenzene-2-carboxylic acid (HABA) assays, luminescence titrations, competitive assays using native biotin, and quenching experiments using methyl viologen. On the basis of the results of these experiments, a homogeneous competitive assay for biotin has been investigated.     

Synthesis, characterization, and reactivity of [Ru(bpy)(CH3CN)3(NO2)]PF6, a synthon for [Ru(bpy)(L3)NO2] complexes

We report a high yield, two-step synthesis of fac-[Ru(bpy)(CH3CN)3NO2]PF6 from the known complex [(p-cym)Ru(bpy)Cl]PF6 (p-cym = eta(6)-p-cymene). [(p-cym)Ru(bpy)NO2]PF6 is prepared by reacting [(p-cymene)Ru(bpy)Cl]PF6 with AgNO3/KNO2 or AgNO2. The 15NO2 analogue is prepared using K15NO2. Displacement of p-cymene from [(p-cym)Ru(bpy)NO2]PF6 by acetonitrile gives [Ru(bpy)(CH3CN)3NO2]PF6. The new complexes [(p-cym)Ru(bpy)NO2]PF6 and fac-[Ru(bpy)(CH3CN)3NO2]PF6 have been fully characterized by 1H and 15N NMR, IR, elemental analysis, and single-crystal structure determination. Reaction of [Ru(bpy)(CH3CN)3NO2]PF6 with the appropriate ligands gives the new complexes [Ru(bpy)(Tp)NO2] (Tp = HB(pz)3-, pz = 1-pyrazolyl), [Ru(bpy)(Tpm)NO2]PF6 (Tpm = HC(pz)3), and the previously prepared [Ru(bpy)(trpy)NO2]PF6 (trpy = 2,2',6',2' '-terpyridine). Reaction of the nitro complexes with HPF6 gives the new nitrosyl complexes [Ru(bpy)TpNO][PF6]2 and [Ru(bpy)(Tpm)NO][PF6]3. All complexes were prepared with 15N-labeled nitro or nitrosyl groups. The nitro and nitrosyl complexes were characterized by 1H and 15N NMR and IR spectroscopy, elemental analysis, cyclic voltammetry, and single-crystal structure determination for [Ru(bpy)TpNO][PF6]2. For the nitro complexes, a linear correlation is observed between the nitro 15N NMR chemical shift and 1/nu(asym), where nu(asym) is the asymmetric stretching frequency of the nitro group.     

Electronic and photophysical properties of adducts of [Ru(bpy)3]2+ and Dawson-type sulfite polyoxomolybdates α/β-[Mo18O54(SO3)2]4-

The spectroscopic and photophysical properties of [Ru(bpy)(3)](2)[[Mo(18)O(54)(SO(3))(2)], where bpy is 2,2'-bipyridyl and [Mo(18)O(54)(SO(3))(2)](4-) is either the α or β-sulfite containing polyoxomolybdate isomer, have been measured and compared with those for the well known but structurally distinct sulfate analogue, α-[Mo(18)O(54)(SO(4))(2)](4-). Electronic difference spectroscopy revealed the presence of new spectral features around 480 nm, although they are weak in comparison with the [Ru(bpy)(3)](2)[Mo(18)O(54)(SO(4))(2)] analogue. Surprisingly, Stern-Volmer plots of [Ru(bpy)(3)](2+) luminescence quenching by the polyoxometallate revealed the presence of both static and dynamic quenching for both α and β-[Mo(18)O(54)(SO(3))(2)](4-). The association constant inferred for the ion cluster [Ru(bpy)(3)](2)α-[Mo(18)O(54)(SO(4))(2)] is K = 5.9 ± 0.56 × 10(6) and that for [Ru(bpy)(3)](2)β-[Mo(18)O(54)(SO(4))(2)] is K = 1.0 ± 0.09 × 10(7). Unlike the sulfate polyoxometalates, both sulfite polyoxometalate-ruthenium adducts are non-luminescent. Despite the strong electrostatic association in the adducts resonance Raman and photoelectrochemical studies suggests that unlike the sulfato polyoxometalate analogue there is no sensitization of the polyoxometalate photochemistry by the ruthenium centre for the sulfite anions. In addition, the adducts exhibit photochemical lability in acetonitrile, attributable to decomposition of the ruthenium complex, which has not been observed for other [Ru(bpy)(3)](2+) -polyoxometalate adducts. These observations suggest that less electronic communication exists between the [Ru(bpy)(3)](2+) and the sulfite polyoxoanions relative to their sulfate polyoxoanion counterparts, despite their structural and electronic analogy. The main distinction between sulfate and sulfite polyoxometalates lies in their reversible reduction potentials, which are more positive by approximately 100 mV for the sulfite anions. This suggests that the capacity for [Ru(bpy)(3)](2+) or analogues to sensitize photoreduction in the adducts of polyoxometalates requires very sensitive redox tuning.     

A donor--acceptor--donor bridging ligand in a class III mixed-valence complex

The novel mononuclear and dinuclear complexes [Ru(trpy)(bpy)(apc)][PF(6)] and [(Ru(trpy)(bpy))(2)(mu-adpc)][PF(6)](2) (bpy = 2,2'-bipyridine, trpy = 2,2':6',2' '-terpyridine, apc(-) = 4-azo(phenylcyanamido)benzene, and adpc(2)(-) = 4,4'-azodi(phenylcyanamido)) were synthesized and characterized by (1)H NMR, UV-vis, and cyclic voltammetry. Crystallography showed that the dinuclear Ru(II) complex crystallizes from diethyl ether/acetonitrile solution as [(Ru(trpy)(bpy))(2)(mu-adpc)][PF(6)](2).2(acetonitrile).2(diethyl ether). Crystal structure data are as follows: crystal system triclinic, space group P1, with a, b, and c = 12.480(2), 13.090(3) and 14.147(3) A, respectively, alpha, beta, and gamma = 79.792(3), 68.027(3), and 64.447(3) degrees, respectively, V = 1933.3(6) A(3), and Z = 1. The structure was refined to a final R factor of 0.0421. The mixed-valence complex with metal ions, separated by a through-space distance of 19.5 A, is a class III system, having the comproportionation constant K(c) = 1.3 x 10(13) and an intervalence band at 1920 nm (epsilon(max) = 10 000 M(-1) cm(-1)), in dimethylformamide solution. The results of this study strongly suggest that the bridging ligand adpc(2-) can mediate metal-metal coupling through both hole-transfer and electron-transfer superexchange mechanisms.