trans-Configured Ligands Boost Spin Crossover to Room Temperature in Mononuclear Fe(II) Complexes.

IF 3.5 3区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Chemistry - An Asian Journal Pub Date : 2025-07-21 DOI:10.1002/asia.202500638

Guang-Wen Fu, Yan Kong, Xin Chen, Ying-Ying Wu, Zi-Han Yan, Zhao-Yang Li, Yan-Hui Shi, Jing-Wei Dai, Xi-Guang Han, Feng-Lei Yang

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引用次数: 0

Abstract

Seven new mononuclear complexes [Fe(aqin)₂(NCS)₂] (1), [Fe(aqin)₂(NCSe)₂] (2), [Fe(aqin)₂(NCBH₃)₂] (3), [Fe(2-pic)₂(NCS)₂] (4), [Fe(2-pic)₂(NCSe)₂] (5), [Fe(2-pic)(NCBH₃)₂] (6), [Fe(tpa)(NCBH₃)₂] (7), [aqin = 8-aminoquinoline, 2-pic = 2-picolylamine, tpa = tris(2-pyridylmethyl)amine)] are investigated. Structurally, except for 3, which affords a trans-configuration, all the complexes adopt a cis-configuration. Their propensity to crystallize without any solvent molecules facilitates the study of the influence of the "pure" ligand on spin-crossover (SCO) characteristics. Magnetically, 1, 2, and 4 remain in the high-spin state, and 3, 5, 6, and 7 display SCO with transition temperatures T_1/2 of approximately 310, 162, 262, and 400 K, respectively. The T_1/2 values of all the complexes except 3 follow the sequence of ligand-field strength, whereas the T_1/2 value of 3 is increased to room temperature, beyond that of the whole cis-[Fe(2-pic)₂(NCE)₂] family. Theoretical modeling based on the harmonic approximation via Gaussian and periodic DFT+U+D3 calculations via the QE reveals that the lower distortion effect of the trans-configuration resulted in the LS stabilization increasing T_1/2.

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反式配体促进单核铁（II）配合物室温自旋交叉。

研究了七种新的单核配合物[Fe(aqin)2(NCS)2] (1), [Fe(aqin)2(NCSe)2] (2), [Fe(aqin)2(NCS)2] (3), [Fe(2-pic)2(NCS)2] (4), [Fe(2-pic)2(NCSe)2] (5), [Fe(2-pic)(NCBH3)2] (6), [Fe(tpa)(NCBH3)2] (7), [aqin = 8-氨基喹啉，2-pic = 2-吡啶胺，tpa =三（2-吡啶甲基）胺]。在结构上，除3为反式外，其余配合物均为顺式。它们在没有任何溶剂分子的情况下结晶的倾向有利于研究“纯”配体对自旋交叉（SCO）特性的影响。在磁性上，1,2,4保持在高自旋状态，3,5,6和7显示SCO，转变温度分别约为310,162,262和400 K。除3外，其余配合物的T1/2值均遵循配体场强度的顺序，而3的T1/2值在室温下增加，超出了整个顺式-[Fe(2-pic)2(NCE)2]家族。基于高斯谐波近似的理论建模和基于QE的周期DFT+U+D3计算表明，反构型的低畸变效应导致LS稳定性增加T1/2。

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

Chemistry - An Asian Journal 化学-化学综合

CiteScore

7.00

自引率

2.40%

发文量

535

审稿时长

1.3 months

期刊介绍： Chemistry—An Asian Journal is an international high-impact journal for chemistry in its broadest sense. The journal covers all aspects of chemistry from biochemistry through organic and inorganic chemistry to physical chemistry, including interdisciplinary topics. Chemistry—An Asian Journal publishes Full Papers, Communications, and Focus Reviews. A professional editorial team headed by Dr. Theresa Kueckmann and an Editorial Board (headed by Professor Susumu Kitagawa) ensure the highest quality of the peer-review process, the contents and the production of the journal. Chemistry—An Asian Journal is published on behalf of the Asian Chemical Editorial Society (ACES), an association of numerous Asian chemical societies, and supported by the Gesellschaft Deutscher Chemiker (GDCh, German Chemical Society), ChemPubSoc Europe, and the Federation of Asian Chemical Societies (FACS).