Ferrer Sacramento, Hernández-Gil Javier, Valverde-Muñoz Francisco Javier, Lloret Francisco, Castiñeiras Alfonso
Departament de Química Inorgànica, Universitat de València Av. Vicent Andrés Estellés, s/n, 46100 Burjassot Valencia Spain
Institut de Ciència Molecular (ICMol), Universitat de València C/Catedrático José Beltrán Martínez, 2, 46980 Paterna Valencia Spain.
RSC Adv. 2019 Sep 17;9(50):29357-29367. doi: 10.1039/c9ra05922a. eCollection 2019 Sep 13.
The asymmetric 3,5-disubstituted 1,2,4-triazole ligand HV (5-amino-3-picolinamido-1,2,4-triazole) by reaction with an excess of Cu(ii) perchlorate (Cu : HV being 12 : 1) has produced a novel hexanuclear {Cu(μ-O/H)(HV/V)} fragment, with one triangular Cu(μ-O/H) group connected to three peripheral single Cu(ii) ions through a -- bridging mode of the ligand, which is the building block of the three structures described here: one hexanuclear, [Cu(μ-O)(HV)(ClO)(HO)]·8HO (1), one dodecanuclear, Cu(μ-O)(V)(ClO)(HO)·6HO (2), and one tetradecanuclear 1D-polymer, {Cu(μ-OH)(V)(HV)(ClO)(HO)·14HO} (3), the last two containing hexanuclear subunits linked by perchlorato bridges. The Cu-Cu av. intra-triangle distance is 3.352(2) Å and the Cu(central)-Cu(bridged external) av. distance is 5.338(3) Å. The magnetic properties of the hexanuclear "CuO-3Cu" cluster have been studied, resulting as best fit parameters: = 2.18(1), (intra-triangle) = -247.0(1) cm and (central Cu - external Cu) = -5.15(2) cm.
不对称的3,5 - 二取代1,2,4 - 三唑配体HV（5 - 氨基 - 3 - 吡啶甲酰胺基 - 1,2,4 - 三唑）与过量的高氯酸铜（铜与HV的比例为12∶1）反应生成了一种新型的六核{Cu(μ - O/H)(HV/V)}片段，其中一个三角形的Cu(μ - O/H)基团通过配体的--桥连模式与三个外围的单个Cu(ii)离子相连，这是此处描述的三种结构的构建单元：一种六核结构，[Cu(μ - O)(HV)(ClO)(HO)]·8HO (1)；一种十二核结构，Cu(μ - O)(V)(ClO)(HO)·6HO (2)；以及一种十四核一维聚合物，{Cu(μ - OH)(V)(HV)(ClO)(HO)·14HO} (3)，后两种结构包含通过高氯酸根桥连的六核亚单元。三角形内Cu - Cu的平均距离为3.352(2) Å，中心Cu(central) - 桥连外部Cu(bridged external)的平均距离为5.338(3) Å。对六核“CuO - 3Cu”簇的磁性进行了研究，得到的最佳拟合参数为： = 2.18(1)，（三角形内） = -247.0(1) cm，（中心Cu - 外部Cu） = -5..15.15(2) cm。
