Coexistence of Two Thermally Induced Intramolecular Electron Transfer Processes in a Series of Metal Complexes [M(Cat‐N‐BQ)(Cat‐N‐SQ)]/[M(Cat‐N‐BQ)2] (M=Co,Fe, and Ni) bearing Non‐Innocent Catechol‐Based Ligands: A Combined Experimental and Theoretical Study |
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| Authors: | Emi Evangelio Dr Marie‐Laure Bonnet Dr Miquel Cabañas Dr Motohiro Nakano Dr Jean‐Pascal Sutter Dr Andrea Dei Prof Vincent Robert Dr Daniel Ruiz‐Molina Dr |
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| Institution: | 1. Centro de Investigación en Nanociencia y Nanotecnología (CIN2, CSIC‐ICN), Edifici CM7, Campus UAB 08193, Cerdanyola del Vallès, Catalonia (Spain), Fax: (+34)?93‐5813717;2. Laboratoire de Chimie, UMR 5182, école normale supérieure de Lyon, 69364 Lyon cedex 07 (France);3. Servei de Ressonància Magnètica Nuclear, UAB, Campus de la UAB 08193, Cerdanyola del Vallès, Catalonia (Spain);4. Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Yamada‐oka, Suita, Osaka 565‐0871 (Japan);5. Laboratoire de Chimie de Coordination du CNRS (CNRS:LCC), 205, route de Narbonne, 31077 Toulouse (France) and Université de Toulouse, UPS, INP, LCC;6. Laboratory of Molecular Magnetism, Dept. of Chemistry, Polo Scientifico, Via della Lastrucia (Italy) |
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| Abstract: | The different thermally induced intermolecular electron transfer (IET) processes that can take place in the series of complexes M(Cat‐N‐BQ)(Cat‐N‐SQ)]/M(Cat‐N‐BQ)2], for which M=Co ( 2 ), Fe ( 3 ) and Ni( 4 ), and Cat‐N‐BQ and Cat‐N‐SQ denote the mononegative (Cat‐N‐BQ?) or dinegative (Cat‐N‐SQ2?) radical forms of the tridentate Schiff‐base ligand 3,5‐di‐tert‐butyl‐1,2‐quinone‐1‐(2‐hydroxy‐3,5‐di‐tert‐butylphenyl)imine, have been studied by variable‐temperature UV/Vis and NMR spectroscopies. Depending on the metal ion, rather different behaviors are observed. Complex 2 has been found to be one of the few examples so far reported to exhibit the coexistence of two thermally induced electron transfer processes, ligand‐to‐metal (IETLM) and ligand‐to‐ligand (IETLL). IETLL was only found to take place in complex 3 , and no IET was observed for complex 4 . Such experimental studies have been combined with ab initio wavefunction‐based CASSCF/CASPT2 calculations. Such a strategy allows one to solicit selectively the speculated orbitals and to access the ground states and excited‐spin states, as well as charge‐transfer states giving additional information on the different IET processes. |
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| Keywords: | electron transfer magnetic properties mixed‐valent compounds radicals valence tautomerism |
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