首页|Controlling Three-Step and Five-Step Spin Transitions by Polymorphism in an FeⅢ Spin Crossover Complex

Controlling Three-Step and Five-Step Spin Transitions by Polymorphism in an FeⅢ Spin Crossover Complex

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Regulating spin crossover(SCO)behavior,especially controlling the spin transition steps,is an important scientific issue,mainly be-cause people aim to control spin bistability and multistability.Presently,SCO bistability can be regulated by changing the lig-and-modifying species,non-coordinated anions,guest molecules,and metal-ion dopant.However,the control of multistability is ex-tremely challenging,especially in Fe(Ⅲ)SCO compounds.Here,we report that[FeⅢ(H-5-Br-thsa)(5-Br-thsa)]·H2O(5-Br-thsa=(5-bromo-2-hydroxybenzylidene)hydrazinecarbothioamide),a compound we have reported before,exists in two polymorphic forms:polymorph 1 exhibits three-step SCO,and polymorph 2 shows five-step SCO,with multi-step SCO behavior effectively regulated by polymorphism.According to single-crystal and powder X-ray diffractometry,polymorphs 1 and 2 crystallize in different space groups during their spin transitions,with two-step symmetry breaking observed(Pbcn → Pnc2 → Pbcn for polymorph 1;P21/n → Pn →P21/n for polymorph 2).We realized that the behavior of these two polymorphs depends significantly on the structure,including(ⅰ)the average Fe-N bond distance,(ⅱ)deformation of octahedral FeⅢ atoms,and(ⅲ)distinct crystal packing,which account for the large differences observed in magnetic properties.

Spin crossoverMulti-step spin transitionSymmetry breakingPolymorphismMagnetic property

Yingying Wu、Shuang Peng、Ziyi Zhang、Yue Gao、Guangyan Xu、Jingwei Dai、Zhao-Yang Li、Masahiro Yamashita

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School of Materials Science and Engineering,Nankai University,38 Tongyan Road,Haihe Educational Park,Tianjin 300350,China

State Key Laboratory of Medicinal Chemical Biology,Nankai University,Tianjin 300071,China

Department of Chemistry,Graduate School of Science,Tohoku University,Sendai 980-8578,Japan

Nankai University for providing startup funds for young talented researchers国家自然科学基金国家自然科学基金国家自然科学基金Ph.D.Candidate Research Innovation Fund of the NKU School of Materials Science and Engineering

219711242227510022150710513

2024

10.1002/cjoc.202300679

中国化学(英文版)
中国化学会 上海有机化学研究所

中国化学(英文版)

CSTPCD
影响因子：0.848
ISSN：1001-604X
年,卷(期)：2024.42(8)
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