Optical electron transfer processes. The dependence of intervalence line shape and transition energy on chromophore concentration

Robert L. Blackbourn; Joseph T. Hupp

doi:10.1016/0009-2614(88)80426-3

Optical electron transfer processes. The dependence of intervalence line shape and transition energy on chromophore concentration

Robert L. Blackbourn^*, Joseph T. Hupp

^*Corresponding author for this work

Chemistry

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

35 Scopus citations

Abstract

Optical electron transfer in the mixed-valence cation of biferrocenylacetylene (BF⁺) has been examined in CD₂Cl₂ solvent. The intervalence absorption line shape is relatively narrow at both low and high chromophore concentrations, but broader at intermediate concentrations. The transition energy for metal-to-metal charge transfer increases from ≈4440 cm^-1 at infinite dilution to 5995 cm^-1 for 3.8 mM BF⁺. Related effects exist due to added electrolyte. Neither the electrolyte nor chromophore concentration effects are expected from a simple reading of electron transfer theories. Nevertheless, both phenomena can be understood and within the context of theory upon careful consideration of the effects of ion-pairing (and tripling) equilibria upon electron-transfer energetics.

Original language	English (US)
Pages (from-to)	399-405
Number of pages	7
Journal	Chemical Physics Letters
Volume	150
Issue number	6
DOIs	https://doi.org/10.1016/0009-2614(88)80426-3
State	Published - Sep 23 1988

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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10.1016/0009-2614(88)80426-3

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title = "Optical electron transfer processes. The dependence of intervalence line shape and transition energy on chromophore concentration",

abstract = "Optical electron transfer in the mixed-valence cation of biferrocenylacetylene (BF+) has been examined in CD2Cl2 solvent. The intervalence absorption line shape is relatively narrow at both low and high chromophore concentrations, but broader at intermediate concentrations. The transition energy for metal-to-metal charge transfer increases from ≈4440 cm-1 at infinite dilution to 5995 cm-1 for 3.8 mM BF+. Related effects exist due to added electrolyte. Neither the electrolyte nor chromophore concentration effects are expected from a simple reading of electron transfer theories. Nevertheless, both phenomena can be understood and within the context of theory upon careful consideration of the effects of ion-pairing (and tripling) equilibria upon electron-transfer energetics.",

author = "Blackbourn, {Robert L.} and Hupp, {Joseph T.}",

note = "Funding Information: This work was supported by the US Department of Energy, OffIce of Energy Research under grant No. DE-FG02-87KR13808. RLB acknowledges support as a Shell Graduate Fellow. We also acknowledge helpful comments from a reviewer and from Profes-sor Michael Weaver.",

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doi = "10.1016/0009-2614(88)80426-3",

language = "English (US)",

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pages = "399--405",

journal = "Chemical Physics Letters",

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T1 - Optical electron transfer processes. The dependence of intervalence line shape and transition energy on chromophore concentration

AU - Blackbourn, Robert L.

AU - Hupp, Joseph T.

N1 - Funding Information: This work was supported by the US Department of Energy, OffIce of Energy Research under grant No. DE-FG02-87KR13808. RLB acknowledges support as a Shell Graduate Fellow. We also acknowledge helpful comments from a reviewer and from Profes-sor Michael Weaver.

PY - 1988/9/23

Y1 - 1988/9/23

N2 - Optical electron transfer in the mixed-valence cation of biferrocenylacetylene (BF+) has been examined in CD2Cl2 solvent. The intervalence absorption line shape is relatively narrow at both low and high chromophore concentrations, but broader at intermediate concentrations. The transition energy for metal-to-metal charge transfer increases from ≈4440 cm-1 at infinite dilution to 5995 cm-1 for 3.8 mM BF+. Related effects exist due to added electrolyte. Neither the electrolyte nor chromophore concentration effects are expected from a simple reading of electron transfer theories. Nevertheless, both phenomena can be understood and within the context of theory upon careful consideration of the effects of ion-pairing (and tripling) equilibria upon electron-transfer energetics.

AB - Optical electron transfer in the mixed-valence cation of biferrocenylacetylene (BF+) has been examined in CD2Cl2 solvent. The intervalence absorption line shape is relatively narrow at both low and high chromophore concentrations, but broader at intermediate concentrations. The transition energy for metal-to-metal charge transfer increases from ≈4440 cm-1 at infinite dilution to 5995 cm-1 for 3.8 mM BF+. Related effects exist due to added electrolyte. Neither the electrolyte nor chromophore concentration effects are expected from a simple reading of electron transfer theories. Nevertheless, both phenomena can be understood and within the context of theory upon careful consideration of the effects of ion-pairing (and tripling) equilibria upon electron-transfer energetics.

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JO - Chemical Physics Letters

JF - Chemical Physics Letters

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Optical electron transfer processes. The dependence of intervalence line shape and transition energy on chromophore concentration

Abstract

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