Solvent Control of Orbital Mixing and Electronic Coupling inLigand-Bridged Mixed-Valence Complexes: Evidence for an Intervalence Hole-Transfer Pathway

Joseph T Hupp

doi:10.1021/ja00160a040

Solvent Control of Orbital Mixing and Electronic Coupling inLigand-Bridged Mixed-Valence Complexes: Evidence for an Intervalence Hole-Transfer Pathway

Joseph T Hupp^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

40 Scopus citations

Abstract

Solvent-induced electronic effects exist for intervalence charge-transfer reactions involving complexes of the type (2,2'-bipyridine)₂ClRu^II(pyrazine)Ru^III(NH₃)₄L⁴⁺, where L = NH₃ or various pyrazyl, pyridyl, or polypyridyl ligands. Specifically the following are found: (1) Mixing between appropriate donor and acceptor metal orbitals can be influenced substantially by the nature of the solvent. (2) The metal-metal interaction energy, H₁₃, is also affected. (3) From the solvent effects, intervalence transfer appears to follow (in part) a hole-transfer pathway.

Original language	English (US)
Pages (from-to)	1563-1565
Number of pages	3
Journal	Journal of the American Chemical Society
Volume	112
Issue number	4
DOIs	https://doi.org/10.1021/ja00160a040
State	Published - Jan 1 1990

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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title = "Solvent Control of Orbital Mixing and Electronic Coupling inLigand-Bridged Mixed-Valence Complexes: Evidence for an Intervalence Hole-Transfer Pathway",

abstract = "Solvent-induced electronic effects exist for intervalence charge-transfer reactions involving complexes of the type (2,2'-bipyridine)2ClRuII(pyrazine)RuIII(NH3)4L4+, where L = NH3 or various pyrazyl, pyridyl, or polypyridyl ligands. Specifically the following are found: (1) Mixing between appropriate donor and acceptor metal orbitals can be influenced substantially by the nature of the solvent. (2) The metal-metal interaction energy, H13, is also affected. (3) From the solvent effects, intervalence transfer appears to follow (in part) a hole-transfer pathway.",

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AB - Solvent-induced electronic effects exist for intervalence charge-transfer reactions involving complexes of the type (2,2'-bipyridine)2ClRuII(pyrazine)RuIII(NH3)4L4+, where L = NH3 or various pyrazyl, pyridyl, or polypyridyl ligands. Specifically the following are found: (1) Mixing between appropriate donor and acceptor metal orbitals can be influenced substantially by the nature of the solvent. (2) The metal-metal interaction energy, H13, is also affected. (3) From the solvent effects, intervalence transfer appears to follow (in part) a hole-transfer pathway.

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