Temperature- and Solvent-Induced Multistep Single-Crystal to Single-Crystal Conversions of Mn(II) Complexes with Diverse Magnetic Properties

IF 3.2 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Crystal Growth & Design Pub Date : 2025-04-21 DOI:10.1021/acs.cgd.5c0008810.1021/acs.cgd.5c00088

Xiaofang Hao, Yu-Xia Wang*, Yue Yang, Zhenjun Song*, Xiaofang Dong, Shen Wang, Yulu Liang, Licun Li and Peng Cheng*,

{"title":"Temperature- and Solvent-Induced Multistep Single-Crystal to Single-Crystal Conversions of Mn(II) Complexes with Diverse Magnetic Properties","authors":"Xiaofang Hao, Yu-Xia Wang*, Yue Yang, Zhenjun Song*, Xiaofang Dong, Shen Wang, Yulu Liang, Licun Li and Peng Cheng*, ","doi":"10.1021/acs.cgd.5c0008810.1021/acs.cgd.5c00088","DOIUrl":null,"url":null,"abstract":"A series of Mn(II) complexes, namely, {(H-2-MI)2[Mn(C5O5)2]}n (1), (H-2-MI)2[Mn(C5O5)2(H2O)2] (2), [Mn(C5O5)(CH3OH)2(H2O)]n (3), [Mn(H2O)3(C5O5)]n (4), and [Mn(2-MI)(C5O5)(H2O)2]n (5), (2-MI = 2-methylimidazole, H2C5O5 = croconic acid), was obtained through a series of multistep single-crystal to single-crystal conversions by modulating external conditions. Notably, 1 and 2 demonstrate reversible interconversion driven by temperature variations, whereas interconversions among 2, 3, 4, and 5 are achieved by altering solvent environment. To assess the feasibility of these conversions, crystal free energy and ligand binding energy calculations were performed to elucidate the underlying mechanism driving the pronounced structural changes, which involve the breaking and reformation of coordination bonds. The conversion mechanism of 1 and 2 is related to free energy, the dispersion-corrected DFT+U calculation shows a 21.075 eV increase in free energy during the conversion. The spontaneous crystal transformations within 2, 3, 4, and 5 are consistent with the ligand binding energy trend. Magnetic measurements were conducted on the stable crystals of 2, 4, and 5. Interestingly, as Mn(II) complexes, 2 exhibited field-induced slow magnetic relaxation behaviors, whereas 4 and 5 displayed no magnetic relaxation dynamics. Further research shows that this slow magnetic relaxation originates from the phonon bottleneck process. The difference of magnetic properties comes from the difference of dimensions and geometric configuration.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 9","pages":"2792–2797 2792–2797"},"PeriodicalIF":3.2000,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Crystal Growth & Design","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.cgd.5c00088","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}

引用次数: 0

Abstract

A series of Mn(II) complexes, namely, {(H-2-MI)₂[Mn(C₅O₅)₂]}_n (1), (H-2-MI)₂[Mn(C₅O₅)₂(H₂O)₂] (2), [Mn(C₅O₅)(CH₃OH)₂(H₂O)]_n (3), [Mn(H₂O)₃(C₅O₅)]_n (4), and [Mn(2-MI)(C₅O₅)(H₂O)₂]_n (5), (2-MI = 2-methylimidazole, H₂C₅O₅ = croconic acid), was obtained through a series of multistep single-crystal to single-crystal conversions by modulating external conditions. Notably, 1 and 2 demonstrate reversible interconversion driven by temperature variations, whereas interconversions among 2, 3, 4, and 5 are achieved by altering solvent environment. To assess the feasibility of these conversions, crystal free energy and ligand binding energy calculations were performed to elucidate the underlying mechanism driving the pronounced structural changes, which involve the breaking and reformation of coordination bonds. The conversion mechanism of 1 and 2 is related to free energy, the dispersion-corrected DFT+U calculation shows a 21.075 eV increase in free energy during the conversion. The spontaneous crystal transformations within 2, 3, 4, and 5 are consistent with the ligand binding energy trend. Magnetic measurements were conducted on the stable crystals of 2, 4, and 5. Interestingly, as Mn(II) complexes, 2 exhibited field-induced slow magnetic relaxation behaviors, whereas 4 and 5 displayed no magnetic relaxation dynamics. Further research shows that this slow magnetic relaxation originates from the phonon bottleneck process. The difference of magnetic properties comes from the difference of dimensions and geometric configuration.

Abstract Image

查看原文本刊更多论文

温度和溶剂诱导的具有不同磁性的Mn（II）配合物的单晶到单晶的多步转化

通过调节外界条件，通过一系列多步单晶到单晶的转化，得到了一系列Mn（II）配合物，即{(H-2-MI)2[Mn(C5O5)2 (H2O)2]}n(1)、（H-2-MI）2[Mn(C5O5)2(H2O)2] n(3)、[Mn(C5O5) 3(C5O5)]n(4)和[Mn(2- mi)(C5O5)(H2O)2]n(5)、（2- mi = 2-甲基咪唑，H2C5O5 = croconic酸）。值得注意的是，1和2在温度变化的驱动下表现出可逆的相互转化，而2、3、4和5的相互转化是通过改变溶剂环境实现的。为了评估这些转换的可行性，进行了晶体自由能和配体结合能的计算，以阐明驱动显著结构变化的潜在机制，其中包括配位键的断裂和重组。1和2的转换机理与自由能有关，经色散校正的DFT+U计算表明，在转换过程中自由能增加了21.075 eV。2、3、4、5内的自发晶体转变与配体结合能趋势一致。对稳定的2、4、5晶体进行了磁测量。有趣的是，作为Mn（II）配合物，2表现出场致慢磁弛豫行为，而4和5没有表现出磁弛豫动力学。进一步的研究表明，这种缓慢的磁弛豫源于声子瓶颈过程。磁性能的差异来自于尺寸和几何构型的不同。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Crystal Growth & Design 化学-材料科学：综合

CiteScore

6.30

自引率

10.50%

发文量

650

审稿时长

1.9 months

期刊介绍： The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials. Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.