首页|Gradual or Hysteretic Transition:Anion Effects on Cobalt(Ⅱ)Spin Crossover Complexes
Gradual or Hysteretic Transition:Anion Effects on Cobalt(Ⅱ)Spin Crossover Complexes
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To better understand the impact of different anions on the structures and SCO properties of the CoⅡ SCO complexes,six new complex-es[Co(terpy-CH2OH)2]A2·sol(terpy-CH2OH=4'-(hydroxymethyl)-2,2';6',2"-terpyridine,A=Br-(1,sol=1.5H2O),I-(2),N3(3,sol=2H2O),H3BCN-(4),OTf-(5),and TsO-(6,sol=4H2O·CH3CN),have been synthesized and characterized.All six compounds consist of mononuclear[Co(terpy-CH2OH)2]2+cations and charge-balancing anions that differ in size,shape,and hydrogen bonding capacity.Complexes 1,2,3,and 6 displayed incomplete gradual SCO transitions,whereas 4 and 5 exhibited abrupt hysteretic spin transitions with loops of 12 and 16 K(250.0-262.0 K for 4,and 370.0-386.0 K for 5,respectively),closely resembling our previously reported complexes with SCN-and SeCN-anions.The occurrence of the order-disorder transition of the CH2OH groups and their transition temperatures are determined by the size and hydrogen bonding capability of the anions.Remarkably,the transition temperatures of complexes with H3BCN-,SCN-,OTf-,and SeCN-anions exhibit an upward trend as the size and mass of the anions increase,as con-firmed through detailed single crystal structure analyses conducted in both high-spin and low-spin states for all four complexes.
Yu-Chen Sun、Ying-Lian Li、Cheng-Cheng Zhang、Feng-Li Chen、Dong Shao、Yue Zhao、Hai-Yan Wei、Xin-Yi Wang
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State Key Laboratory of Coordination Chemistry,Collaborative Innovation Center of Advanced Microstructures,School of Chemistry and Chemical Engineering,Nanjing University,Nanjing,Jiangsu 210023,China
Hubei Key Laboratory of Processing and Application of Catalytic Materials,College of Chemistry and Chemical Engineering,Huanggang Normal University,Huanggang,Hubei 438000,China
Jiangsu Key Laboratory of Biofunctional Materials,School of Chemistry and Materials Science,Nanjing Normal University,Nanjing,Jiangsu 210023,China
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