Optical and thermal charge-transfer processes occurring in a series of three-centered, cyanide-bridged intervalent charge-transfer complexes

Brian W. Pfennig, Andrew Bruce Bocarsly

Research output: Contribution to journalArticlepeer-review

45 Scopus citations

Abstract

The mixed-valent compound {Pt(NH3)4}2{(NC)5Fe-CN-Pt(NH 3)4-NC-Fe(CN)5} was used as the starting point for the synthesis and characterization of two series of trinuclear "M-Pt-M" compounds. The first group of complexes have the general formula Na2{L(NC)4Fe-CN-Pt(NH3) 4-NC-Fe(CN)4L} (where the sixth coordination site on the terminal iron units has been varied using six different substituted pyridine or pyrazine ligands, L), and the secondary group of compounds have the general formula {Pt(NH3)4}2{(NC)5M-CN-Pt(NH 3)4-NC-M(CN)5} (where M = Fe, Ru, and Os). All of the compounds yielded an absorption spectrum containing an intervalent charge-transfer (IT) band in the visible. Both series of complexes were modeled using Marcus-Hush theory to estimate the reorganization energies for the optical electron-transfer processes, electron-transfer rate constants, thermal-activation barriers, and the degrees of delocalization of these species. In addition, the kinetics of formation, photochemical decomposition, and a novel solvent-gated charge-transfer process are discussed.

Original languageEnglish (US)
Pages (from-to)226-233
Number of pages8
JournalJournal of Physical Chemistry
Volume96
Issue number1
DOIs
StatePublished - Jan 1 1992

All Science Journal Classification (ASJC) codes

  • Engineering(all)
  • Physical and Theoretical Chemistry

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