NH/pi interaction in a spin-crossover complex [FeII(HLMe)2](BPh4)2.2CH3CN (BPh4-=Tetraphenylborate; HLMe=2-Methylimidazol-4-yl-methylideneamino-2-ethylpyridine) |
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Authors: | Arata Shinobu Torigoe Haruna Iihoshi Tomotaka Matsumoto Naohide Dahan Françoise Tuchagues Jean-Pierre |
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Institution: | Department of Chemistry, Faculty of Science, Kumamoto University, Kurokami 2-39-1, Kumamoto 860-8555, Japan. |
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Abstract: | Three FeII complexes, Fe(HLR)2](BPh4)2.solvent (R=H, Me, Ph), were synthesized, where BPh4-=tetraphenylborate and HLR=2-substituted-imidazol-4-yl-methylideneamino-2-ethylpyridine. The magnetic susceptibility measurements in 5-300 K revealed that Fe(HLH)2](BPh4)2.H2O, Fe(HLMe)2](BPh4)2.2CH3CN, and Fe(HLPh)2](BPh4)2.CH3CN are low-spin (LS), spin-crossover (SC), and high-spin (HS) FeII complexes, respectively, indicating that the spin state can be effectively tuned by the bulkiness of the substituent. Complex shows a steep SC around 250 K, where it assumes a cyclic structure of {Fe(HLMe)2]BPh4}2 constructed by four NH/pi bonds between the imidazole group and the phenyl ring of BPh4- in the HS state and a deformed structure with NH/pi bonds and linear CH3CN...HN hydrogen bonds at the terminals in the LS state. |
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