Su Cheng-Yong, Cai Yue-Peng, Chen Chun-Long, Smith Mark D, Kaim Wolfgang, zur Loye Hans-Conrad
School of Chemistry and Chemical Engineering, Zhongshan University, Guangzhou 510275, People's Republic of China.
J Am Chem Soc. 2003 Jul 16;125(28):8595-613. doi: 10.1021/ja034267k.
Three angular ditopic ligands (1,3-bis(benzimidazol-1-ylmethyl)-4,6-dimethylbenzene L(1), 1,3-bis(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene L(2), and 1,4-bis(benzimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene L(3)) and one tripodal ligand 1,3,5-tris(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene L(4) have been prepared. Reaction of these shape-specific designed ligands with different metal salts affords a series of discrete molecular architectures: Ag(2)L(1)(2)(2) 1, Ag(2)L(2)(2)(2) 2, [CF(3)SO(3)(-) subset Ag(2)L(3)(2)]CF(3)SO(3) 3, [CF(3)SO(3)(-) subset Ag(2)L(3)(3)]CF(3)SO(3) 4, ClO(4)(-) subset Cu(2)L(2)(4)(3) 5, [4H(2)O subset Ni(2)L(2)(4)Cl(4)].6H(2)O 6, BF(4)(-) subset Ag(3)L(4)(2)(2) 7, ClO(4)(-) subset Ag(3)L(4)(2)(2) 8, and CuI(3)(2-) subset Cu(3)L(4)(2)[Cu(2)I(4)] 9. The compounds were characterized by elemental analysis, ESI-MS, IR, and NMR spectroscopy, and X-ray crystallography. 1 is a dinuclear metallacycle with 2-fold rotational symmetry in which two syn-conformational L(1) ligands are connected by two linearly coordinated Ag(+) ions. 2 and 3 are structurally related, consisting of rectangular structures assembled from two linearly coordinated Ag(+) ions and two L(2) or L(3) ligands. The structure of 4 is a trigonal prismatic box consisting of two Ag(+) ions in trigonal planar coordination linked by three L(3) ligands, while the structures of 5 and 6 are tetragonal prismatic cages constructed by two square planar Cu(2+) or Ni(2+) ions linked by four L(2) ligands. The topologies of 7-9 are similar to that of 4; however, these three structures are assembled from three linearly coordinated Ag(+) or Cu(+) ions and two tripodal ligands, representing an alternative strategy to assembling a trigonal prism. (1)H NMR and ESI-MS were utilized to elucidate the solution structures of these macrocycles.
已制备出三种角形双齿配体（1,3 - 双（苯并咪唑 - 1 - 基甲基） - 4,6 - 二甲基苯L(1)、1,3 - 双（苯并咪唑 - 1 - 基甲基） - 2,4,6 - 三甲基苯L(2)和1,4 - 双（苯并咪唑 - 1 - 基甲基） - 2,3,5,6 - 四甲基苯L(3)）以及一种三脚架配体1,3,5 - 三（苯并咪唑 - 1 - 基甲基） - 2,4,6 - 三甲基苯L(4)。这些形状特异性设计的配体与不同金属盐反应得到了一系列离散的分子结构：Ag(2)L(1)(2)(2) 1、Ag(2)L(2)(2)(2) 2、[CF(3)SO(3)(-)⊂Ag(2)L(3)(2)]CF(3)SO(3) 3、[CF(3)SO(3)(-)⊂Ag(2)L(3)(3)]CF(3)SO(3) 4、ClO(4)(-)⊂Cu(2)L(2)(4)(3) 5、[4H({2})O⊂Ni(2)L(2)(4)Cl(4)].6H({2})O 6、BF(4)(-)⊂Ag(3)L(4)(2)(2) 7、ClO(4)(-)⊂Ag(3)L(4)(2)(2) 8和CuI(3)(2 - )⊂Cu(3)L(4)(2)[Cu(2)I(4)] 9。通过元素分析、电喷雾电离质谱（ESI - MS）、红外光谱（IR）、核磁共振光谱（NMR）以及X射线晶体学对这些化合物进行了表征。1是具有2重旋转对称性的双核金属环，其中两个顺式构象的L(1)配体由两个线性配位的Ag(+)离子连接。2和3在结构上相关，由两个线性配位的Ag(+)离子和两个L(2)或L(3)配体组装而成的矩形结构组成。4的结构是一个三角棱柱形盒子，由三个L(3)配体连接的处于三角平面配位的两个Ag(+)离子组成，而5和6的结构是由四个L(2)配体连接的两个平面正方形Cu(2+)或Ni(2+)离子构成的四方棱柱形笼子。7 - 9的拓扑结构与4相似；然而，这三种结构由三个线性配位的Ag(+)或Cu(+)离子和两个三脚架配体组装而成，代表了一种组装三角棱柱的替代策略。利用核磁共振氢谱（^{1}H NMR）和电喷雾电离质谱（ESI - MS）阐明了这些大环化合物的溶液结构。
