卤氢键桥联的铁(Ⅲ)配合物呈现出高于室温的自旋交叉行为  

A Halogen Hydrogen-Bonded Fe(Ⅲ)Complex Showing Hysteretic Spin-Crossover Behavior above Room Temperature

作　　者：卫晓琴 高转 任帆 崔晓友 周悦 邵东 WEI Xiao‑Qin;GAO Zhuan;REN Fan;CUI Xiao‑You;ZHOU Yue;SHAO Dong(Shanxi Province Collaborative Innovation Center for Light Materials Modification and Application,Department of Material Science and Engineering,Jinzhong University,Jinzhong,Shanxi 030619,China;Hubei Key Laboratory of Processing and Application of Catalytic Materials,College of Chemistry and Chemical Engineering,Huanggang Normal University,Huanggang,Hubei 438000,China;State Key Laboratory of Coordination Chemistry,Nanjing University,Nanjing 210023,China)

机构地区：[1]晋中学院材料科学与工程系,山西省轻质材料改性应用协同创新中心,晋中030619 [2]黄冈师范学院化学化工学院,催化材料制备及应用湖北省重点实验室,黄冈438000 [3]南京大学配位化学国家重点实验室,南京210023

出　　处：《无机化学学报》2022年第11期2283-2290,共8页Chinese Journal of Inorganic Chemistry

基　　金：山西省基础研究计划(自由探索类)项目(No.20210302123355);山西省高等学校科技创新项目(No.2020L0592);晋中学院博士基金项目(No.jzxybsjjxm2019020);黄冈师范学院启动基金(No.2042021033);配位化学国家重点实验室开放基金项目(No.SKLCC2208)资助。

摘　　要：使用一个三齿配体2,6-二(苯并咪唑-2-基)吡啶(bzimpy)与三价铁离子反应,制备了一例单核的铁配合物[Fe~Ⅲ(bzimpy-1H)_(2)]Cl(1)(bzimpy-1H为bzimpy脱去一个质子后的产物),并对其结构和磁性质进行了详细表征。单晶结构分析表明配合物中Fe中心处于畸变的N_(6)八面体配位环境,相邻的阳离子配合物基元与抗衡氯离子通过N—H…Cl氢键作用构建了超分子的三维结构。磁性研究和差示扫描量热法研究表明,配合物表现出高于室温的磁滞自旋交叉(SCO)行为(T_(1/2)↑=345 K,T_(1/2)↓=330 K)并且观察到低温光诱导激发自旋态捕获(LIESST)效应。磁构关系研究表明,氯氢键对配合物的双稳态SCO行为具有重要的作用。A mononuclear Fe(Ⅲ)complex,[Fe^(Ⅲ)(bzimpy-1H)_(2)]Cl(1)was prepared by the reaction of a tridentate ligand 2,6-bis(benzimidazol-2-yl)pyridine(bzimpy),where bzimpy-1H is the product of bzimpy after removing one proton,and its structure and magnetic properties were characterized in detail.The single crystal structure analysis shows that the Fe^(3+)center features a rare distorted octahedral N6coordination environment for the complex,and the 3D supramolecular structure is constructed by N—H…Cl hydrogen bonding between the adjacent cation complex units and counterbalance chloride ions.The complex showed hysteretic spin-crossover(SCO)behavior above room temperature as evidenced by combined magnetic investigations and differential scanning calorimetry measurements(T_(1/2)↑=345 K,T_(1/2)↓=330 K).In addition,the light-induced excited spin state trapping(LIESST)effect was also observed in the complex.The magnetism-structure relationship shows that the N—H…Cl hydrogen bonding plays an important role in the bistable SCO behavior of the complex.CCDC:2164316.

关 键 词：自旋交叉 铁配合物 双稳态 氢键 超分子作用 

分 类 号：O614.811[理学—无机化学]