Gu Zhi-Guo, Zuo Jing-Lin, You Xiao-Zeng
Coordination Chemistry Institute and the State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, PR China.
Dalton Trans. 2007 Sep 28(36):4067-72. doi: 10.1039/b708789f. Epub 2007 Aug 21.
Two novel three-dimensional coordination polymers Cu(6)(N(3))(12)(N-Eten)(2) (1) (N-Eten=N-ethylethylenediamine) and {[Cu(9)(N(3))(18)(1,2-pn)(4)].H(2)O}(n) (2) (1,2-pn=1,2-diaminopropane) have been synthesized by the self-assembly reactions of Cu(NO(3))(2).3H(2)O, NaN(3) and small diamine ligands. Their molecular structures were determined by single-crystal X-ray diffraction. Complex 1 is composed of a neutral 3D coordination framework based on unprecedented hexanuclear copper(ii) clusters which features three types of bridging modes for azide (mu-1,1, mu-1,3 and mu-1,1,3). Complex 2 is a novel 3D coordination polymer featuring octanuclear copper-azido clusters and Cu(diamine)(2) units which are linked by azido bridges. Magnetic studies for complex show ferromagnetic ordering at 3.5 K, where the azido bridges mediate ferromagnetic coupling between adjacent Cu(II) ions. The magnetic data for 1 were fitted to a uniform hexanuclear copper model which yielded g=2.21, J=6.26 cm(-1), zJ'=0.39 cm(-1). Complex 2 shows ferromagnetic coupling in the octanuclear unit and antiferromagnetic interaction between neighboring units.
通过硝酸铜三水合物（Cu(NO₃)₂·3H₂O）、叠氮化钠（NaN₃）与小分子二胺配体的自组装反应，合成了两种新型三维配位聚合物[Cu₆(N₃)₁₂(N - Eten)₂]ₙ（1）（N - Eten = N - 乙基乙二胺）和{[Cu₉(N₃)₁₈(1,2 - pn)₄]·H₂O}ₙ（2）（1,2 - pn = 1,2 - 二氨基丙烷）。通过单晶X射线衍射确定了它们的分子结构。配合物1由基于前所未有的六核铜（II）簇的中性三维配位框架组成，该框架具有三种类型的叠氮桥连模式（μ - 1,1、μ - 1,3和μ - 1,1,3）。配合物2是一种新型三维配位聚合物，其特征是八核铜 - 叠氮簇和通过叠氮桥连接的[Cu(二胺)₂]²⁺单元。对配合物的磁性研究表明，在3.5 K时存在铁磁有序，其中叠氮桥介导相邻Cu（II）离子之间的铁磁耦合。配合物1的磁性数据拟合到一个均匀的六核铜模型，得到g = 2.21，J = 6.26 cm⁻¹，zJ' = 0.39 cm⁻¹。配合物2在八核单元中显示铁磁耦合，在相邻单元之间显示反铁磁相互作用。
