A cobalt(III)-polydioxolene polymer undergoing valence tautomeric interconversion was irradiated at cryogenic temperatures. Magnetic and EPR data suggest the occurrence of photoinduced VT interconversion, with a maximum degree of about 10%. The kinetics data evidence a larger amount of cooperativity than previously observed in simple monomer, a phenomenon that we attribute to the ID nature of the system. In the range 9-40 K the relaxation time follows two different regimes, both temperature dependent. The small values of the activation energies suggest the existence of phonon assisted relaxation mechanisms based on a tunneling process involving the total-symmetric breathing mode of the complex.

Ligand design modulates photoinduced properties of cobalt-dioxolene valence tautomers / A. Beni; A. Dei; D. A. Shultz; L. Sorace. - In: CHEMICAL PHYSICS LETTERS. - ISSN 0009-2614. - STAMPA. - 428:(2006), pp. 400-404. [10.1016/j.cplett.2006.07.054]

Ligand design modulates photoinduced properties of cobalt-dioxolene valence tautomers

DEI, ANDREA;SORACE, LORENZO
2006

Abstract

A cobalt(III)-polydioxolene polymer undergoing valence tautomeric interconversion was irradiated at cryogenic temperatures. Magnetic and EPR data suggest the occurrence of photoinduced VT interconversion, with a maximum degree of about 10%. The kinetics data evidence a larger amount of cooperativity than previously observed in simple monomer, a phenomenon that we attribute to the ID nature of the system. In the range 9-40 K the relaxation time follows two different regimes, both temperature dependent. The small values of the activation energies suggest the existence of phonon assisted relaxation mechanisms based on a tunneling process involving the total-symmetric breathing mode of the complex.
2006
428
400
404
A. Beni; A. Dei; D. A. Shultz; L. Sorace
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Utilizza questo identificatore per citare o creare un link a questa risorsa: https://hdl.handle.net/2158/344886
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