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液晶锌(II)和铁(II)烷基三唑一维配位聚合物。

Liquid-crystalline zinc(II) and iron(II) alkyltriazoles one-dimensional coordination polymers.

机构信息

CNRS, CRPP, UPR 8641, F-33600 Pessac, France.

出版信息

Inorg Chem. 2012 May 7;51(9):5417-26. doi: 10.1021/ic300404r. Epub 2012 Apr 9.

Abstract

Several series of unidimensional coordination polymers of formula Zn(C(n)H(2n+1)trz)(3)(2)·xH(2)O (n = 18, 16, 13, 11, 10, trz = 4-substituted-1,2,4-triazole), Zn(C(18)H(37)trz)(3)(2)·xH(2)O, Fe(C(n)H(2n+1)trz)(3)(2)·xH(2)O (n = 18, 16, 13, 10; X = Cl(-) or ptol(-), where ptol(-) = p-tolylsulfonate anion), and Fe(C(18)H(37)trz)(3)(2)·xH(2)O (X = C(8)H(17)PhSO(3)(-) and C(8)H(17)SO(3)(-)) are reported with their thermal, structural, and magnetic properties. Most of these materials exhibit thermotropic lamellar mesophases at temperatures as low as 410 K, as confirmed by textures observed by polarized optical microscopy. The corresponding phase diagrams deduced by differential scanning calorimetry are also reported. All iron-containing materials present a spin crossover phenomenon that occurs at temperatures ranging from 242 to 360 K, only slightly below the mesophase temperature domain, and remains complete and cooperative, even for the longer alkyl substituents. The use of stable diamagnetic Zn(II) analogues proves to be very useful to characterize the comparatively less stable and less crystalline Fe(II) analogues.

摘要

几种一维配位聚合物的系列,通式为Zn(C(n)H(2n+1)trz)(3)(2)·xH(2)O(n = 18,16,13,11,10,trz = 4-取代-1,2,4-三唑),Zn(C(18)H(37)trz)(3)(2)·xH(2)O,Fe(C(n)H(2n+1)trz)(3)(2)·xH(2)O(n = 18,16,13,10;X = Cl(-)或 ptol(-),其中 ptol(-) = p-甲苯磺酸根阴离子),和Fe(C(18)H(37)trz)(3)(2)·xH(2)O(X = C(8)H(17)PhSO(3)(-)和 C(8)H(17)SO(3)(-)),这些材料都具有热学、结构和磁性特性。这些材料中的大多数在低至 410 K 的温度下就表现出热致层状介晶相,这一现象通过偏光显微镜观察到的纹理得到证实。还报道了相应的差示扫描量热法相图。所有含铁材料都呈现出自旋交叉现象,该现象发生在 242 到 360 K 的温度范围内,仅略低于介晶相温度范围,并且即使对于较长的烷基取代基,仍然是完整的和协同的。使用稳定的抗磁性 Zn(II)类似物证明对相对不稳定和结晶性较差的 Fe(II)类似物进行特征描述非常有用。

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