Ligand design modulates photoinduced properties of cobalt-dioxolene valence tautomers

Beni, A.; Dei, Andrea; Shultz, D. A.; Sorace, Lorenzo

doi:10.1016/j.cplett.2006.07.054

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.

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Titolo:	Ligand design modulates photoinduced properties of cobalt-dioxolene valence tautomers
Autori di Ateneo:	A. Beni DEI, ANDREA D. A. Shultz SORACE, LORENZO mostra contributor esterni nascondi contributor esterni
Autori:	A. Beni; DEI, ANDREA; D. A. Shultz; SORACE, LORENZO
Anno di registrazione:	2006
Rivista:	CHEMICAL PHYSICS LETTERS
Volume:	428
Pagina iniziale:	400
Pagina finale:	404
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.
Handle:	http://hdl.handle.net/2158/344886
Appare nelle tipologie:	1a - Articolo su rivista

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