Light-Induced Electron Transfer Reactions of Hydrophobic Analogs of Ru(bipy)<sub>3</sub><sup>2+</sup>

DeLaive, Patricia J.; Lee, J. T.; Abruña, Héctor D.; Sprintschnik, Hertha W.; Meyer, Thomas J.; Whitten, David G.

doi:10.1021/ba-1978-0168.ch002

Cited by 29 publications

(19 citation statements)

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“…Some of the effects produced by micelles may have their origin in changes in the steric and nonadiabatic factors. Evidence for the operation of such factors in the absence of micelles is provided by the reactions of a series of Ru(bpy(COOR)2)32+ complexes in organic solvents (46)(47)(48).…”

Section: Plot Of Potential Energy Versus Nuclear Configuration For (A)mentioning

confidence: 99%

“…Ru(bpy)32+ or 34bpy(COOR))32+, TEA. Ru(bpy)32+ and the hydrophobic ruthenium(II) complex Ru(bpy(COOR))341 where R is the isopropyl group are reductively quenched by triethylamine (TEA) in water-aceconitrile mixtures (46) . The TEA radical produced in the quenching step rapidly reacts with TEA to form a very reducing radical (47) (compare the TEOA and EDTA radical reactions mentioned earlier).…”

Section: Hydrogen Formation Reactionsmentioning

confidence: 99%

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Light induced electron transfer reactions of metal complexes

Sutin¹,

Creutz²

1980

Pure and Applied Chemistry

234

125

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Properties of the excited states of tris(2,2'-bipyridine) and tris(l,lO-phenanthroline) complexes of chromium(III), iron(II), ruthenium(II), osmium(II), rhodium(III), and iridium(III) are described. The electron transfer reactions of the ground and excited states are discussed and interpreted in terms of the driving force for the reaction and the distortions of the excited states relative to the corresponding g.-ound states. General considerations relevant to the conversion of light into chemical energy are presented and progress in the use of polypyridine cot:~plexes to effect the light induced decomposition of ••ater into hydrogen and oxygen is reviewed.~e excited state~ are of three types: metal-centered ligand-field (M (d-d)) excited states ( Cr(bpy)J3+ and Fe(bp~)J2+), metal-to-ligand charge-transfer (MLCT) excited states ( *Ru~bpy)J2+, *os(bpy)J +), and intraligand (L( rr -rr*) ) excited states ( *Rh(phen)J3+ and Ir ( bpy)J3+). The nature of *cuLz+ is not known, but it has been postulated to be an MLCT state ( 8).

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Section: Plot Of Potential Energy Versus Nuclear Configuration For (A)mentioning

confidence: 99%

Section: Hydrogen Formation Reactionsmentioning

confidence: 99%

Light induced electron transfer reactions of metal complexes

Sutin¹,

Creutz²

1980

Pure and Applied Chemistry

234

125

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“…Importantly, the combination between electronic substituent effect of the isopropyl acetate group and C-HO interactions in 4 provide relatively high cooperativity, which leads to an abrupt SCO behavior. and diisopropyl-2,2'-bipyridine-5,5'-dicarboxylate (i-PrObpydc) 20 were prepared following literature procedures. Powder samples for 1-4 were prepared by similar procedures described in the literature (Scheme 2).…”

Section: Introductionmentioning

confidence: 99%

Spin Crossover Behavior in a Homologous Series of Iron(II) Complexes Based on Functionalized Bipyridyl Ligands

et al. 2018

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A series of bulky substituted bipyridine-related iron(II) complexes [Fe(HBpz)(L)] (pz = pyrazolyl) were prepared, where L = 5,5'-dimethyl-2,2'-bipyridine (bipy-CH, 1), L = dimethyl-2,2'-bipyridyl-5,5'-dicarboxylate (MeObpydc, 2), L = diethyl-2,2'-bipyridyl-5,5'-dicarboxylate (EtObpydc, 3), or L = diisopropyl-2,2'-bipyridine-5,5'-dicarboxylate ( i-PrObpydc, 4). The crystal structures of five new iron(II) complexes were determined by X-ray diffraction: those of 1, 3, and 4 and two modifications of 3 (3B) and 4 (4B). Complexes 1 and 3B display incomplete spin crossover (SCO) behavior because of a freezing-in effect, whereas 3 and 4B undergo gradual and incomplete SCO behaviors. Complexes 2 and 4 show a completely gradual and steep SCO, respectively. Such different SCO behaviors can be attributed to an electronic substituent effect in the bipyridyl ligand conformation and a crystal packing effect. Importantly, the electronic substituent effect of the isopropyl acetate group and C-H···O supramolecular interactions in 4 contribute to a highly cooperative behavior, which leads to an abrupt thermally induced spin transition.

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“…It being a shame to waste all those potentially perfectly good solar photons, approaches must be taken to improve the absorption characteristics of the medium, especially to the red; there is no lack of chromophores + , substitution of phen (=1,10-phenanthroline) for bpy or substitution on the polypyridyl rings has little effect on X max or the shape of the visible absorption envelope (26,27). Some red shift of X max to 473 and 501 nm is observed for Ru(terpy)^+ and Ru(TPTZ)^+ (terpy = 2,2',2"^terpyridine; TPTZ = 2,4,6-tri(2-pyridyl-s-triazine)) (26).…”

Section: -1 -1mentioning

confidence: 99%

“…By assuming that differences in shape, size, solution, and entropy of the ground and excited states are small, the redox potentials of the excited state are fairly well approximated by equations 5 and 6 (43). (27,34) which can result in variations of k' of more than a factor of 10 when below the diffusion-controlled plateau (45).…”

Section: Formation Of Separated Charge Carriersmentioning

confidence: 99%

Photochemical Determinants of the Efficiency of Photogalvanic Conversion of Solar Energy

Hoffman

Lichtin

1979

Solar Energy

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A photogalvanic cell is a battery in which the cell solution absorbs light directly to generate species which, upon back reaction through an external circuit with the aid of suitable electrodes, produces electric power; photoactivation of the electrodes is 'not involved. The charge-carrying species have storage capacity if they are long-lived and can be prevented from engaging in degradativc back reactions in bulk solution. The efficiency of a photogalvanic cell for the conversion of photon energy into electrical energy is determined by photochemical and electrochemical factors. Among the latter are the choice of electrode materials and the kinetics of electron transfer at the heterogeneous surfaces. In this paper we examine '"the photochemical determinants of the efficiency of photogalvanic eel] operation: the absorption spectral characteristics of the cell solution, the efficiency of formation of separated charge carriers, and the lifetimes of the carriers toward back electron transfer. Modulation of bulk solution dynamics can be achieved by variation of the solution medium. The photochemical determinants are discussed with particular reference to the use of thionine or Ru(bpy)2+ as the light absorbing species.

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Light-Induced Electron Transfer Reactions of Hydrophobic Analogs of Ru(bipy)₃²⁺

Cited by 29 publications

References 0 publications

Light induced electron transfer reactions of metal complexes

Light induced electron transfer reactions of metal complexes

Spin Crossover Behavior in a Homologous Series of Iron(II) Complexes Based on Functionalized Bipyridyl Ligands

Photochemical Determinants of the Efficiency of Photogalvanic Conversion of Solar Energy

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Light-Induced Electron Transfer Reactions of Hydrophobic Analogs of Ru(bipy)32+

Cited by 29 publications

References 0 publications

Light induced electron transfer reactions of metal complexes

Light induced electron transfer reactions of metal complexes

Spin Crossover Behavior in a Homologous Series of Iron(II) Complexes Based on Functionalized Bipyridyl Ligands

Photochemical Determinants of the Efficiency of Photogalvanic Conversion of Solar Energy

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Light-Induced Electron Transfer Reactions of Hydrophobic Analogs of Ru(bipy)₃²⁺