具有三角架结构的丙二酸、β-二酮和吡唑衍生物的合成、结构及超分子自组装

本文系统的探讨了1,3,5-丙二酸衍生物取代基（2-5），戊烷-2,4-二酮取代基(6)，3,5-二甲基-1H-吡唑取代基-2,4,6-三乙基苯(7)的合成和结构。1H NMR分析表明，这些化合物在溶液中具有高度的对称性；X-单晶衍射分析确认这些化合物在固态均采取1,3,5-交替构象，即三个功能取代基团处在中心苯环平面的一边，而三个乙基则位于该中心苯环平面的另一边。分子内和分子间氢键是化合物4,5,7实现超分子自组装的主要作用力。化合物7（L）的吡唑取代基与铜离子（II）通过Cu-N的配位键作用形成笼状配合物8 (Cu3L2)，在配合物8中，两配体分子7（L）采取了顺式面面相向的构象。

Synthesis,Structures and Self-assemblies of Tripodal Malonate, β-Diketones and Pyrazolyls Derivatives

Tripodal 1,3,5-tris(2-methylenemalonic acid)-2,4,6-triethyllbenzene derivatives 2-5, 1,3,5-tris(2-methylenepentane-2,4-dione)-2,4,6-triethyllbenzene 6 and 1,3,5-tri((3,5- dimethyl-1H-pyrazol-4-yl)methyl)-2,4,6-triethylbenzene 7 have been synthesized. 1H NMR spectra of these compounds are in accord with that they are all in high levels of symmetry. Single crystal X-ray structure analysis revealed that they all adopt an 1,3,5-alternate conformation with the three functional arms reside on one side of the benzene plane, and the three ethyl groups are placed on the opposite side of the benzene plane. Intermolecular hydrogen-bond interactions are the major driving force for the solid state assembly of the compounds with malonic acid (4), malonamide (5), as well as 3,5-dimethyl-1H-pyrazolyl (7) functions. However, No molecular capsules were formed by these compounds via intermolecular hydrogen-bond interactions in the solid state. The interaction of copper(II) ions and pyrazolyl-containing compound 7 (L) resulted in the formation of a discrete cylindrical cage-like complex (Cu3L2) 8 via C-N coordination bonds by the connection of three Cu2+ ions and six pyrazolyl nitrogen atoms from two 7 ligands. The two ligands 7 in complex 8 are in a cis,cis,cis-conformation and a face-to-face orientation.