Details

Autor(en) / Beteiligte

• Beni, Alessandra
• Dei, Andrea
• Shultz, David A.
• Sorace, Lorenzo

Titel

Ligand design modulates photoinduced properties of cobalt-dioxolene valence tautomers

Ist Teil von

• Chemical physics letters, 2006-09, Vol.428 (4), p.400-404

Ort / Verlag

Elsevier B.V

Erscheinungsjahr

2006

Quelle

Access via ScienceDirect (Elsevier)

Beschreibungen/Notizen

• Magnetic and EPR data suggest the occurrence of photoinduced Valence Tautomerism in a cobalt(III)-polydioxolene polymer. The 1D nature of the system results in a larger amount of cooperativity than previously observed in monomers. Analysis of kinetics data further suggest the existence of a relaxation mechanisms based on phonon assisted tunnelling. 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 1D 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 totalsymmetric breathing mode of the complex.