Du Miao, Bu Xian-He, Guo Ya-Mei, Ribas Joan
Department of Chemistry, Nankai University, Tianjin 300071, China.
Chemistry. 2004 Mar 19;10(6):1345-54. doi: 10.1002/chem.200305300.
The construction of two unique, high-nuclearity Cu(II) supramolecular aggregates with tetrahedral or octahedral cage units, (mu(3)-Cl)Li subset Cu(4)(mu-L(1))(3)(8)(H(2)O)(4.5) (1) and Na(2) subset Cu(12)(mu-L(2))(8)(mu-Cl)(4)(8)(H(2)O)(10)(H(3)O(+))(2) (2) by alkali-metal-templated (Li(+) or Na(+)) self-assembly, was achieved by the use of two newly designed carboxylic-functionalized diazamesocyclic ligands, N,N'-bis(3-propionyloxy)-1,4-diazacycloheptane (H(2)L(1)) or 1,5-diazacyclooctane-N,N'-diacetate acid (H(2)L(2)). Complex 1 crystallizes in the trigonal R3c space group (a = b = 20.866(3), c = 126.26(4) A and Z = 12), and 2 in the triclinic P1 space group (a = 13.632(4), b = 14.754(4), c = 19.517(6) A, alpha = 99.836(6), beta = 95.793(5), gamma = 116.124(5) degrees and Z = 1). By subtle variation of the ligand structures and the alkali-metal templates, different polymeric motifs were obtained: a dodecanuclear architecture 1 consisting of three Cu(4) tetrahedral cage units with a Li(+) template, and a supramolecular chain 2 consisting of two crystallographically nonequivalent octahedral Cu(6) polyhedra with a Na(+) template. The effects of ligand functionality and alkali metal template ions on the self-assembly processes of both coordination supramolecular aggregates, and their magnetic behaviors are discussed in detail.
通过碱金属模板（Li⁺或Na⁺）自组装构建了两种独特的、具有高核性的含四面体或八面体笼单元的Cu(II)超分子聚集体，即(μ₃-Cl)[Li⊂Cu₄(μ-L₁)₃]₃₈(H₂O)₄.₅ (1)和[Na₂⊂Cu₁₂(μ-L₂)₈(μ-Cl)₄₈(H₂O)₁₀(H₃O⁺)₂]∞ (2)，这是通过使用两种新设计的羧基官能化二氮杂环配体N,N'-双(3-丙酰氧基)-1,4-二氮杂环庚烷(H₂L₁)或1,5-二氮杂环辛烷-N,N'-二乙酸(H₂L₂)实现的。配合物1结晶于三方晶系R3c空间群（a = b = 20.866(3)，c = 126.26(4) Å且Z = 12），配合物2结晶于三斜晶系P1空间群（a = 13.632(4)，b = 14.754(4)，c = 19.517(6) Å，α = 99.836(6)，β = 95.793(5)，γ = 116.124(5)°且Z = 1）。通过配体结构和碱金属模板的细微变化，得到了不同的聚合物结构单元：由三个带有Li⁺模板的Cu₄四面体笼单元组成的十二核结构1，以及由两个具有Na⁺模板的晶体学上不等价的八面体Cu₆多面体组成的超分子链2。详细讨论了配体官能团和碱金属模板离子对两种配位超分子聚集体自组装过程及其磁行为的影响。
