College of Chemistry, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Tianjin Normal University, Tianjin, 300387, PR China.
Dalton Trans. 2011 Oct 21;40(39):10082-9. doi: 10.1039/c1dt10958h. Epub 2011 Sep 2.
Three new paramagnetic ion-directed coordination frameworks, {[Co(4)(H(2)O)(2)(μ(3)-OH)(2)(atz)(2)(nip)(2)]·3H(2)O}(n) (1), {[Mn(4)(H(2)O)(2)(μ(3)-OH)(2)(atz)(2)(nip)(2)]·H(2)O·MeOH}(n) (2) and {[Cu(2)(H(2)O)(μ(3)-OH)(atz)(nip)]·2H(2)O}(n) (3), were, respectively, obtained by solvo-/hydrothermal reactions of 5-amino-1H-tetrazole (Hatz), 5-nitroisophathalic acid (H(2)nip) with an inorganic Co(II), Mn(II) or Cu(II) salt. The former two complexes are two-dimensional (2D) covalent layers built from butterfly-shaped tetranuclear M(4)(μ(3)-OH)(2) clusters and double atz(-) and nip(2-) linkers. Whereas complex 3 is a 3D framework with scarcely observed corner-sharing Cu(3)(μ(3)-OH) Δ-chains extended by nip(2-) linkages, in which the anionic atz(-) ligand acts as a reinforcement to consolidate the Δ-chain. Magnetically, due to the interplay of the anisotropy of spin carrier and magnetic exchange interactions from the adjacent spin carriers, the complexes exhibit spin-canted antiferromagnetism with a Néel temperature lower than 2.0 K for 1 and an antiferromagnetic ordering with a slight field-induced spin-flop transition for 2. In contrast, complex 3 with a local Kagomé sublattice displays spin-frustrated antiferromagnetic behavior with magnetic ordering at 16.0 K.
三个新的顺磁离子导向配位骨架，[{[Co(4)(H2O)(2)(μ3-OH)2(atz)2(nip)2]·3H2O}n] (1)、[{[Mn(4)(H2O)(2)(μ3-OH)2(atz)2(nip)2]·H2O·MeOH}n] (2)和[{[Cu(2)(H2O)(μ3-OH)(atz)(nip)]·2H2O}n] (3)，分别通过 5-氨基-1H-四唑（Hatz）、5-硝基异邻苯二甲酸（H2nip）与无机 Co(II)、Mn(II)或 Cu(II)盐的溶剂/水热反应得到。前两个配合物是由蝶形四核 M4(μ3-OH)2 簇和双 atz(-)和 nip(2-)连接体构建的二维（2D）共价层。而配合物 3 是一个具有几乎没有观察到的角共享 Cu(3)(μ3-OH)Δ-链的 3D 骨架，由 nip(2-)连接体扩展，其中阴离子 atz(-)配体作为加固剂来巩固Δ-链。在磁性方面，由于自旋载体的各向异性和相邻自旋载体之间的磁交换相互作用的相互作用，配合物表现出自旋倾斜反铁磁性，对于 1 来说，奈尔温度低于 2.0 K，对于 2 来说，存在微弱的场诱导自旋翻转的反铁磁有序。相比之下，具有局部 Kagomé 亚晶格的配合物 3 表现出自旋受挫反铁磁行为，在 16.0 K 时存在磁有序。
