Halogen Bonds-enhanced Spin Dynamics: Investigating Co-crystallization Effects on Spin Crossover in Mononuclear Mn(III) Schiff-base Complexes

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions Pub Date : 2025-05-17 DOI:10.1039/d5dt00841g

Sheng-Ze Zhao, Liwen Chen, Hai Zhu, Hao-Zhe Zhang, Chang Liu, Chun-Yan Qin, Hai-Ying Wang, Yong-Hua Li, Shi Wang

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引用次数: 0

Abstract

We present co-crystallization with 1,3,5-trifluoro-2,4,6-triiodobenzene (TFTIB) as an approach to tuning spin crossover (SCO) properties of mononuclear Mn(III) Schiff-base complexes. The isostructural complexes [Mn(naphth-sal-N-1,5,8,12)]Y (Y= Br (1) and Y=I (2) and (naphth-sal-N-1,5,8,12)2− is a big conjugated hexadentate Schiff-base ligand) share similar magnetic behaviors and among them complex 2 shows a gradual SCO with transition temperature T1/2 ~ 380 K. Complexes [Mn(naphth-sal-N-1,5,8,12)]∙TFTIB∙Y (Y= Br (3) and Y=I (4)) are synthesized by the co-crystallization of their parent complexes 1 and 2 with the TFTIB and they both exhibit more gradual SCO with T1/2 rising to over 400 K. For comparison, complex [Mn(5-F-sal-N-1,5,8,12)]∙2TFTIB∙Br∙CH3CN (5) was also synthesized, which maintains a high spin (HS) state over the measured temperature range. An anion-TFTIB network connected by halogen-halogen bonds has a significant influence on cation-anion crystal packing and finally the cooperative effects of the SCO complexes.

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卤素键增强的自旋动力学：研究单核Mn（III）席夫碱配合物中自旋交叉的共结晶效应

我们提出了与1,3,5-三氟-2,4,6-三碘苯（TFTIB）共结晶作为调整单核Mn（III）希夫碱配合物自旋交叉（SCO）性质的方法。同构配合物[Mn（萘-盐- n -1,5,8,12）]Y (Y= Br(1)和Y=I（2)和（萘-盐- n -1,5,8,12）2−是一种大共轭六齿希夫碱配体）具有相似的磁性行为，其中配合物2在转变温度T1/2 ~ 380 K时表现为逐渐SCO。配合物[Mn（萘-盐- n -1,5,8,12）]∙TFTIB∙Y (Y= Br（3)和Y=I(4)）是由其母体配合物1和2与TFTIB共结晶合成的，随着T1/2上升到400 K以上，它们都表现出更缓慢的SCO。为了比较，还合成了配合物[Mn(5- f -sal- n -1,5,8,12)]∙2TFTIB∙Br∙CH3CN(5)，该配合物在测量温度范围内保持高自旋（HS）状态。由卤素键连接的阴离子- tftib网络对阳离子-阴离子晶体的填充以及SCO配合物的协同效应有显著影响。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Dalton Transactions 化学-无机化学与核化学

CiteScore

6.60

自引率

7.50%

发文量

1832

审稿时长

1.5 months

期刊介绍： Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.