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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Triazolate-based 3D frameworks and a 2D layer with centrosymmetric Cu-7(II), Cu-5(II), Cu-4(II) clusters and tunable interlayer/interchain compactness: hydrothermal syntheses, crystal structures and magnetic properties
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Triazolate-based 3D frameworks and a 2D layer with centrosymmetric Cu-7(II), Cu-5(II), Cu-4(II) clusters and tunable interlayer/interchain compactness: hydrothermal syntheses, crystal structures and magnetic properties

机译：基于三唑盐的3D框架和具有中心对称的Cu-7（II），Cu-5（II），Cu-4（II）簇和可调的层间/链间紧密度的2D层：水热合成，晶体结构和磁性

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Four 1,2,3-triazolate-based coordination polymers (CPs) with varied dimensionality, different nuclearity numbers and core topologies, [Cu-4(mu-OH)(mu(3)-OH)(ta)(2)(btec)](n) (1), {[Cu-6(mu(3)-OH)(2)(ta)(8)(tp)]center dot 2.5H(2)O}(n) (2), {[Cu-5(mu(3)-OH)(2)(ta)(4)(ip)(2)]center dot 2H(2)O}(n) (3) and {[Cu-5(mu-OH)(2)(mu(3)-OH)(2)(ta)(2)(pa)(2)]center dot 2H(2)O}(n) (4) (ta = 1,2,3-triazolate, btec = 1,2,4,5-benzenetetracarboxylate, tp = terephthalate, ip = isophthalate and pa = phthalate), were hydrothermally synthesized by varying the numbers and positions of the carboxylate group appended on the phenyl tether, and structurally and magnetically characterized. The former three entities are three-dimensional (3D) robust frameworks with a (4(4).6(2))(4(11).6(5))(2)(4(13).6(10).8(5)) topological net containing centro-symmetric Cu-7(II) clusters, square-planar Cu-1(II) cores and tetratopic btec(4-) linkers for 1, a pillared-layered structure consisting of Cu-5(II) + Cu-1(II)-based coplanar layers and ditopic tp(2-) pillars for 2 as well as a micro-porous architecture derived from Cu-5(II) clusters and directional ip(2-) connectors for 3. In contrast, complex 4 exhibits an undulated two-dimensional (2D) layer with alternating Cu-4(II) + Cu-1(II) chains interconnected by anionic pa(2-) connectors. Crystallographically, the increment of the local nuclearity from Cu-4(II) up to Cu-7(II) in 1-4 benefits greatly from the synergistic co-coordination of the hydroxyl group and the coplanar ta(-) ligand towards the metal ion, and the interlayer/interchain compactness is significantly tuned by the position isomerism of the dicarboxylate moieties. Due to the antiferromagnetic coupling in the local clusters and the asymmetric superexchange by mu(3)-ta(-) mediator, these complexes exhibit different spin ground states (paramagnetic S = 1 and 1/2, ferrimagnetic S = 1/2 as well as spin canting) at low temperatures, which are informative for polynuclear-based magnetic materials.
机译：四个1,2,3-三唑盐基配位聚合物（CP），具有不同的尺寸，不同的核数和核心拓扑，[Cu-4（mu-OH）（mu（3）-OH）（ta）（2） btec）]（n）（1），{[Cu-6（mu（3）-OH）（2）（ta）（8）（tp）]中心点2.5H（2）O}（n）（2 ），{[Cu-5（mu（3）-OH）（2）（ta）（4）（ip）（2）]中心点2H（2）O}（n）（3）和{[Cu- 5（mu-OH）（2）（mu（3）-OH）（2）（ta）（2）（pa）（2）]中心点2H（2）O}（n）（4）（ta =通过改变连接在苯基上的羧酸酯基团的数量和位置进行水热合成1,2,3-三唑酸酯，btec = 1,2,4,5-苯四羧酸酯，tp =对苯二甲酸酯，ip =间苯二甲酸酯和pa =邻苯二甲酸酯）。系绳，并在结构和磁性上具有特征。前三个实体是具有（4（4）.6（2））（4（11）.6（5））（2）（4（13）.6（10）的三维（3D）鲁棒框架.8（5））拓扑网，包含中心对称的Cu-7（II）簇，方平面的Cu-1（II）核和四位btec（4-）接头，构成1，由Cu-组成的分层结构5（II）+基于Cu-1（II）的共面层和2的对位tp（2-）支柱以及源自Cu-5（II）簇和定向ip（2-）连接器的微孔结构相比之下，复合物4的波峰二维（2D）层具有交替的Cu-4（II）+ Cu-1（II）链，通过阴离子pa（2-）连接器互连。晶体学上，1-4中从Cu-4（II）到Cu-7（II）的局部核的增加极大地受益于羟基和共平面ta（-）配体对金属的协同配位离子，并且层间/链间的紧密度通过二羧酸酯部分的位置异构性显着调节。由于局部簇中的反铁磁耦合和mu（3）-ta（-）介体的不对称超交换，这些配合物表现出不同的自旋基态（顺磁性S = 1和1/2，亚铁磁性S = 1/2以及（例如自旋倾斜），这对多核基磁性材料很有用。

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