Spin-crossover behavior in two new supramolecular isomers.
Spin-crossover behavior in two new supramolecular isomers.
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DOI：
10.1021/ic402096s
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发表时间：
2014-01
影响因子：
4.6
通讯作者：
Zheng Yan;Z. Ni;Fu-Sheng Guo;Jin-Yan Li;Yanzhen Chen;Jun‐Liang Liu;Wei-Quan Lin;D. Aravena
中科院分区：
文献类型：
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作者：
Zheng Yan;Z. Ni;Fu-Sheng Guo;Jin-Yan Li;Yanzhen Chen;Jun‐Liang Liu;Wei-Quan Lin;D. Aravena
两个自旋交叉（SCO）超分子异构体[Fe(Mebpt){Au(CN)2}]n·xH2O （1, x = 0，和2·H2O， x = n, MebptH = 3-（5-甲基-2-吡啶基）-5-（2-吡啶基）-1,2,4-三唑）已被成功分离，并通过单晶x射线晶体学、热重分析、差示扫描量热法、变温粉末x射线衍射和磁测量进行了表征。结构分析表明，1为二维配位层，2·H2O为一维配位阶梯结构，其中Mebpt（-）配体分别在1和2·H2O中以反式和顺式桥接方式配位。引人注目的是，它们的SCO性质进一步受到Fe（II）的八面体配位构型的影响。在1中，只有反式结构的Fe（II）中心表现出自旋跃迁（Tc = 303 K），而在2·H2O和脱水的2中，分别出现了逐渐的两步SCO行为（Tc1 = 235 K, Tc2 = 313 K）和一步SCO行为（Tc = 315 K）。
Two spin-crossover (SCO) supramolecular isomers formulated as [Fe(Mebpt){Au(CN)2}]n·xH2O (1, x = 0, and 2·H2O, x = n, MebptH = 3-(5-methyl-2-pyridyl)-5-(2-pyridyl)-1,2,4-triazole) have been successfully isolated and characterized by single-crystal X-ray crystallography, thermogravimetric analysis, differential scanning calorimetry, variable-temperature powder X-ray diffraction, and magnetic measurements. Structural analysis reveals that 1 is a two-dimensional coordination layer and 2·H2O is a one-dimensional coordination ladder structure, in which the Mebpt(-) ligands are coordinated in trans and cis bridging mode in 1 and 2·H2O, respectively. Dramatically, their SCO properties are further influenced by the octahedral coordination configuration of Fe(II). In 1, only the Fe(II) centers in trans configuration exhibit spin transition (Tc = 303 K), while in 2·H2O and the dehydrated 2, gradual two-step SCO (Tc1 = 235 K, Tc2 = 313 K) and one-step SCO behaviors (Tc = 315 K) occur, respectively.