Polyhedron Pub Date : 2023-11-29 , DOI: 10.1016/j.poly.2023.116757
Hao-Zhe Zhang , Hua-Wei Zhou , Peng-Yu Xu , Chun-Yan Qin , Sheng-Ze Zhao , Yong-Hua Li , Shi Wang
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Spin crossover (SCO), as a molecular bistable phenomenon, has attracted extensive interest. In this paper, the syntheses, crystal structures and magnetic properties of three Mn(III) hexadentate Schiff-base complexes [Mn(3-OMe-sal-N-1,5,8,12)]AsF6·H2O (1), [Mn(4-OMe-sal-N-1,5,8,12)]AsF6·H2O (2) and [Mn(5-OMe-sal-N-1,5,8,12)]AsF6 (3) have been reported. The substituent positions of ligands and solvent molecules have a cooperative effect on SCO behavior. Complex 1 shows a complete SCO between the high-spin (HS, S = 2) and low-spin (LS, S = 1) states without thermal hysteresis, and complex 2 shows a gradual incomplete SCO behavior. The transition temperatures of 2 (T1/2 = 241 K) is 98 K higher than that of 1 (T1/2 = 143 K), which indicates that the ligand field strength of (4-OMe-sal-N-1,5,8,12)2– is stronger than that of (3-OMe-sal-N-1,5,8,12)2–. Due to the absence of crystallizing solvent water molecule, complex 3 maintains a HS state in the test temperature range.
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配体取代基位置和溶剂对基于六齿希夫碱配体的 Mn(III) 配合物自旋交叉的协同影响
自旋交叉(SCO)作为一种分子双稳态现象,引起了广泛的兴趣。本文研究了三种Mn(III)六齿席夫碱配合物[Mn(3-OMe-sal-N-1,5,8,12)]AsF 6 · H 2 O ( 1) , [Mn(4-OMe-sal-N-1,5,8,12)]AsF 6 ·H 2 O (2)和 [Mn(5-OMe-sal-N-1,5,8, 12)]AsF 6 (3)已被报道。配体和溶剂分子的取代基位置对SCO行为具有协同作用。配合物1显示了高自旋(HS,S = 2)和低自旋(LS,S = 1)状态之间的完整 SCO,没有热滞后,配合物2显示了逐渐不完整的 SCO 行为。2 ( T 1/2 = 241 K)的转变温度 比1 ( T 1/2 = 143 K) 高 98 K,这表明 (4-OMe-sal-N-1 的配体场强,5,8,12) 2–比 (3-OMe-sal-N-1,5,8,12) 2–更强。由于不存在结晶溶剂水分子,配合物3在测试温度范围内保持HS状态。