Effect of pressure-induced freezing on the energy of the intervalence transfer electronic absorption band of binuclear mixed-valence complexes

✍ Scribed by W.S. Hammack; H.G. Drickamer; M.D. Lowery; D.N. Hendrickson

• Publisher: Elsevier Science
• Year: 1986
• Tongue: English
• Weight: 439 KB
• Volume: 132
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(86)80113-0

✦ Synopsis

The Marcus continuum mode1 for the solvent reorientation contribution to the energetics of outer-sphere electron transfer has often been used to analyze the energy of the intervalence transfer (IT) electronic absorption band for a binuclear mixed-valence transition-metal complex. Eel,, the energy required to transfer an electron optically in a mixed-valence complex, was measured as a function of pressure for two binuclear mixed-valence complexes in different solvents which freeze at 25°C under pressures < 10 kbar. Essentially no shifts of the IT bands were observed, indicating the inadequacy of the dielectric continuum mode1 for such complexes.