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Solvent effects on charge transfer bands of nitrogen-centered intervalence compounds

Nelsen, Stephen F. and Trieber, Dwight A., II and Ismagilov, Rustem F. and Teki, Yoshio (2001) Solvent effects on charge transfer bands of nitrogen-centered intervalence compounds. Journal of the American Chemical Society, 123 (24). pp. 5684-5694. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20130821-160728530

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Abstract

Electron transfer parameters are extracted from the optical spectra of intervalence bis(hydrazine) radical cations. Compounds with 2-tert-butyl-3-phenyl-2,3-diazabicyclo[2.2.2]octyl-containing charge-bearing units that are doubly linked by 4-σ-bond and by 6-σ-bond saturated bridges are compared with ones having tert-butylisopropyl- and diphenyl-substituted charge bearing units and others having the aromatic units functioning as the bridge. Solvent effect studies show that the optical transition energy (E_(op)) does not behave as dielectric continuum theory predicts but that solvent reorganization energy may be usefully separated from the vibrational reorganization energy by including linear terms in both the Pekar factor (γ) and the Gutmann donor number (DN) in correlating the solvent effect. Solvation of the bridge for these compounds is too large to ignore, which makes dielectric continuum theory fail to properly predict solvent effects on either E_(op) or the free energy for comproportionation.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja003436nDOIArticle
http://pubs.acs.org/doi/full/10.1021/ja003436nPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja003436nPublisherSupporting Information
ORCID:
AuthorORCID
Ismagilov, Rustem F.0000-0002-3680-4399
Additional Information:Copyright © 2001 American Chemical Society. Published In Issue: June 20, 2001. Received September 19, 2000. Revised Manuscript Received February 6, 2001. We thank the National Science Foundation (Grants CHE-9417946 and CHE-9988727) and the Research Corporation (Grant RA0269) for partial financial support of this research. Supporting Information Available: Tables of solvent parameters employed, cyclic voltammetric data, and variable temperature optical data. This material is available free of charge via the Internet at http://pubs.acs.org.
Funders:
Funding AgencyGrant Number
NSFCHE-9417946
NSFCHE-9988727
Research CorporationRA0269
Subject Keywords:electron-transfer-reactions; ruthenium ammine complexes; coupling matrix-elements; transfer rate constants; reorganization energy; radical cations; mulliken-hush; polar liquids; exchange; temperature
Issue or Number:24
Record Number:CaltechAUTHORS:20130821-160728530
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20130821-160728530
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:40851
Collection:CaltechAUTHORS
Deposited By: Whitney Barlow
Deposited On:28 Aug 2013 21:57
Last Modified:03 Oct 2019 05:43

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