Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 16, Issue 22, Pages 6666-6677Publisher
WILEY-BLACKWELL
DOI: 10.1002/chem.200902568
Keywords
electron transfer; magnetic properties; mixed-valent compounds; radicals; valence tautomerism
Categories
Funding
- Spanish Government [MAT 2009-3977-C03-03]
- Network of Excellence MAGMAnet
- Comunitat de Treball dels Pirineus/Communaute de Travail des Pyrenees program
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The different thermally induced intermolecular electron transfer (IET) processes that can take place in the series of complexes [M(Cat-NBQ)(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 di-negative (Cat-N-SQ(2-)) radical forms of the tridentate Schiff-base ligand 3,5-ditert-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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