单核锰（III）自旋交叉配合物中分子内和分子间相互作用的动态相互作用。

The dynamic interplay between intramolecular and intermolecular interactions in mononuclear manganese(III) SCO complexes.

作者信息

Qin Chun-Yan, Zhao Sheng-Ze, Wu Hua-Yu, Li Yong-Hua, Wang Zi-Kun, Wang Zheng, Wang Shi

机构信息

State Key Laboratory for Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, Nanjing 210023, China.

College of Chemistry and Chemical Engineering, Key Laboratory of Chemical Additives for China National Light Industry, Shaanxi University of Science and Technology, Xi'an 710021, China.

出版信息

Dalton Trans. 2021 May 4;50(17):5899-5910. doi: 10.1039/d0dt04109b.

DOI:10.1039/d0dt04109b

PMID:33949401

Abstract

The effect of counter anions on thermally induced manganese(iii)-based SCO within the [Mn(5-F-sal-N-1,5,8,12)]Y family has been investigated. All the complexes are crystallized without any lattice solvents. Crystal packing and intermolecular forces influence the spin-state stabilization and spin-transition profiles. Magnetic measurements indicate that salts with octahedral anions, [Mn(5-F-sal-N-1,5,8,12)]PF6 (1), [Mn(5-F-sal-N-1,5,8,12)]AsF6 (2) and [Mn(5-F-sal-N-1,5,8,12)]SbF6 (3), show HS electronic configurations between 2 and 300 K, and there exist π-π stackings between the phenyl groups from the neighboring [Mn(5-F-sal-N-1,5,8,12)]+ cations. As for the tetrahedral anions, complex [Mn(5-F-sal-N-1,5,8,12)]BF4 (4) exhibits a gradual and incomplete spin conversion. Complex [Mn(5-F-sal-N-1,5,8,12)] ClO4 (5) shows a nearly complete SCO with T1/2 = 100 K. The remaining salts with spherical anions form Nam-HX (X = Cl, Br, I) hydrogen bonds between Mn(iii) cations and counterions. Complexes [Mn(5-F-sal-N-1,5,8,12)]Cl (6) and [Mn(5-F-sal-N-1,5,8,12)] Cl0.28Br0.72 (7) feature gradual SCO behaviors with T1/2 = 220 K and 235 K, respectively. Complex [Mn(5-F-sal-N-1,5,8,12)]I (8) exhibits a more gradual spin conversion and is far from a complete HS state with a χMT value of 1.89 cm3 mol-1 K at 400 K.

摘要

研究了抗衡阴离子对[Mn(5-F-sal-N-1,5,8,12)]Y家族内热诱导的基于锰(III)的自旋交叉(SCO)的影响。所有配合物结晶时均无晶格溶剂。晶体堆积和分子间作用力影响自旋态稳定性和自旋转变曲线。磁性测量表明，含有八面体阴离子的盐，[Mn(5-F-sal-N-1,5,8,12)]PF6 (1)、[Mn(5-F-sal-N-1,5,8,12)]AsF6 (2)和[Mn(5-F-sal-N-1,5,8,12)]SbF6 (3)，在2至300 K之间呈现高自旋(HS)电子构型，相邻的[Mn(5-F-sal-N-1,5,8,12)]+阳离子的苯基之间存在π-π堆积。至于四面体阴离子，配合物[Mn(5-F-sal-N-1,5,8,12)]BF4 (4)表现出逐渐且不完全的自旋转换。配合物[Mn(5-F-sal-N-1,5,8,12)]ClO4 (5)表现出近乎完全的自旋交叉，T1/2 = 100 K。其余含有球形阴离子的盐在锰(III)阳离子和抗衡离子之间形成Nam-HX (X = Cl、Br、I)氢键。配合物[Mn(5-F-sal-N-1,5,8,12)]Cl (6)和[Mn(5-F-sal-N-1,5,8,12)]Cl0.28Br0.72 (7)分别具有T1/2 = 220 K和235 K的逐渐自旋交叉行为。配合物[Mn(5-F-sal-N-1,5,8,12)]I (8)表现出更逐渐的自旋转换，在400 K时χMT值为1.89 cm3 mol-1 K，远未达到完全的高自旋状态。