Orbital specific charge transfer distances, solvent reorganization energies, and electronic coupling energies: Electronic stark effect studies of parallel and orthogonal intervalence transfer in (NC)5Os(II)-CN- Ru(III)(NH3)5-

Laba Karki, Joseph T. Hupp

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

For the mixed-valent chromophore, (NC)5Os(II)-CN-Ru(III)(NH3)5-, spin-orbit coupling and ligand-field asymmetry effects lead to multiple visible region intervalence (metal-to-metal) charge transfer transitions (Forlando et al. Inorg. Chim. Acta 1994, 223, 37). The higher energy transition is associated with transfer from an Os 5dπ orbital that is nominally orthogonal to the charge transfer axis. The lower energy transition, on the other hand, involves a degenerate pair of Os 5dπ donor orbitals directed along the charge transfer axis. Low-temperature electronic Stark effect measurements of the partially resolved transitions permit donor- orbital-specific one-electron-transfer distances to be directly evaluated. The distances, R, are remarkably dependent upon donor orbital orientation (R(parallel) = 2.8 ± 0.2 Å; R(orthogonal) = 4.0 ± 0.4 Å) and significantly shorter than simple geometric estimates (5.0 Å). From the distance information, donor-orbital-specific coupling energies and solvent reorganization energies can also be estimated. These also differ substantially from those obtained by equating the charge transfer distance with the geometric donor/acceptor separation distance.

Original languageEnglish
Pages (from-to)4070-4073
Number of pages4
JournalJournal of the American Chemical Society
Volume119
Issue number17
DOIs
Publication statusPublished - Apr 30 1997

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Fingerprint Dive into the research topics of 'Orbital specific charge transfer distances, solvent reorganization energies, and electronic coupling energies: Electronic stark effect studies of parallel and orthogonal intervalence transfer in (NC)<sub>5</sub>Os(II)-CN- Ru(III)(NH<sub>3</sub>)<sub>5</sub><sup>-</sup>'. Together they form a unique fingerprint.

  • Cite this