Zhao Liang, Wan Chong-Qing, Han Jie, Chen Xu-Dong, Mak Thomas C W
Department of Chemistry and Center of Novel Functional Molecules, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong SAR, Peoples Republic of China.
Chemistry. 2008;14(33):10437-44. doi: 10.1002/chem.200800968.
Supramolecular networks constructed with the tBu--C[triple bond]C superset Ag(n) (n=4 or 5) metal-ligand synthon and trifluoroacetate have been transformed through the introduction of ancillary terminal nitrile ligands, from acetonitrile through propionitrile to tert-butyronitrile, giving rise to a 2D coordination network in AgC[triple chemical bond]CtBu3 AgCF(3)CO(2)H(2)O (1), a 2D hydrogen-bonded network in AgC[triple chemical bond]CtBu5 AgCF(3)CO(2)4 CH(3)CNH(2)O (2), a 2D hybrid coordination/hydrogen-bonded network in AgC[triple chemical bond]CtBu3 AgCF(3)CO(2)CH(3)CH(2)CN2 H(2)O (3), and another 2D coordination network in AgC[triple chemical bond]CtBu4 AgCF(3)CO(2) (CH(3))(3)CCN2 H(2)O (4). Concomitantly, the linkage modes between adjacent ethynide-bound Ag(n) aggregates in these compounds are also changed. A layer-type hydrogen-bonded host lattice in isostructural AgC[triple chemical bond]CtBu4 AgCF(3)CO(2)(R(4)N)(CF(3)CO(2)) 2 H(2)O (R(4)=BnMe(3), 5; R(4)=Et(4), 6; R(4)=nPr(4), 7) is obtained by introducing quaternary ammonium cations as guest templates, which occupy the interstices and thereby mediate the interlayer separation. Use of the bulky nBu(4)N(+) cation leads to disruption of the host network in AgC[triple bond]CtBu4 AgCF(3)CO(2)3[(nBu(4)N)(CF(3)CO(2))]H(2)O (8) with generation of a discrete dense nido-Ag(5) cluster.
由叔丁基-C≡C超集Ag(n)（n = 4或5）金属-配体合成子与三氟乙酸根构建的超分子网络，通过引入辅助末端腈配体，从乙腈经丙腈到叔丁腈进行了转变，从而在AgC≡CtBu₃ AgCF₃CO₂H₂O（1）中形成二维配位网络，在AgC≡CtBu₅ AgCF₃CO₂·4CH₃CN·H₂O（2）中形成二维氢键网络，在AgC≡CtBu₃ AgCF₃CO₂CH₃CH₂CN·2H₂O（3）中形成二维混合配位/氢键网络，以及在AgC≡CtBu₄ AgCF₃CO₂(CH₃)₃CCN·2H₂O（4）中形成另一个二维配位网络。同时，这些化合物中相邻乙炔基键合的Ag(n)聚集体之间的连接模式也发生了变化。通过引入季铵阳离子作为客体模板，在同构的AgC≡CtBu₄ AgCF₃CO₂(R₄N)(CF₃CO₂)·2H₂O（R₄ = BnMe₃，5；R₄ = Et₄，6；R₄ = nPr₄，7）中获得了层状氢键主体晶格，这些阳离子占据空隙并由此调节层间间距。使用体积较大的nBu₄N⁺阳离子导致AgC≡CtBu₄ AgCF₃CO₂·3[(nBu₄N)(CF₃CO₂)]·H₂O（8）中的主体网络破坏，并生成离散的密集巢式Ag₅簇。
