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Spin Crossover Behavior of Dinuclear Fe II Complexes with Bis‐Tetradentate Bridging‐Type Ligands
Author(s) -
Kanegawa Shinji,
Kang Soonchul,
Sato Osamu
Publication year - 2013
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201201069
Subject(s) - chemistry , spin crossover , pyrazine , crystallography , thermal hysteresis , solvent , spin transition , spin states , bridging ligand , stereochemistry , inorganic chemistry , crystal structure , organic chemistry , phase transition , physics , quantum mechanics
The preparation and characterization of two new Fe II dinuclear complexes with bis‐tetradentate bridging‐type ligands [{Fe(NCS) 2 } 2 (L)] · DMF · 2H 2 O ( 1 : L = L1{2,5‐bis[ N , N ‐bis(2‐pyridylmethyl)aminomethyl]pyrazine}, 2 : L = L2{2,3‐bis[ N , N ‐bis(2‐pyridylmethyl)aminomethyl]pyrazine}) are reported. Magnetic measurements reveal that complexes 1 and 2 exhibit different thermal spin‐crossover behavior. Complex 1 shows a crystalline solvent effect on spin crossover (SCO). After desorption of the crystalline solvent by heating, an abrupt one‐step transition with a hysteresis loop was observed for the desolvated form 1′ . Conversely, a gradual two‐step SCO was obtained for 2 . The photomagnetic effect was also investigated in 1′ and 2 , and both complexes clearly show light‐induced excited spin state trapping. Interestingly, one‐step and two‐step thermal relaxation were observed for 1′ and 2 , respectively. Such different SCO properties occur because of the cooperative effects owing to the structure of the ligand.