Atencio Reinaldo, Linares Marciel M, González Teresa, Briceño Alexander
Laboratorio de Síntesis y Caracterización de Nuevos Materiales, Centro de Química, Instituto Venezolano de Investigaciones Científicas (IVIC), Apto. 21827, Caracas 1020-A, Venezuela.
Acta Crystallogr C Struct Chem. 2024 Sep 1;80(Pt 9):487-496. doi: 10.1107/S2053229624007897. Epub 2024 Aug 19.
The synthesis and structural characterization of four novel supramolecular hydrogen-bonded arrangements based on self-assembly from molecular `[Cu(2,2'-biimidazole)]' modules and malonate anions are presented, namely, tetrakis(2,2'-biimidazole)di-μ-chlorido-dimalonatotricopper(II) pentahydrate, [Cu(CHO)Cl(CHN)]·5HO or [Cu(Hbiim)(μ-Cl)Cu(mal)]·5HO, aqua(2,2'-biimidazole)malonatocopper(II) dihydrate, [Cu(CHO)(CHN)(HO)]·2HO or [Cu(Hbiim)(mal)(HO)]·2HO, bis[aquabis(2,2'-biimidazole)copper(II)] dimalonatodiperchloratocopper(II) 2.2-hydrate, [Cu(CHN)(HO)][Cu(CHO)(ClO)]·2.2HO or [Cu(Hbiim)(HO)][Cu(mal)(ClO)]·2.2HO, and bis(2,2'-biimidazole)copper(II) bis[bis(2,2'-biimidazole)(2-carboxyacetato)malonatocopper(II)] tridecahydrate, [Cu(CHN)][Cu(CHO)(CHO)(CHN)]·13HO or [Cu(Hbiim)][Cu(Hbiim)(Hmal)(mal)]·13HO. These assemblies are characterized by self-complementary donor-acceptor molecular interactions, demonstrating a recurrent and distinctive pattern of hydrogen-bonding preferences among the carboxylate, carboxylic acid and N-H groups of the coordinated 2,2'-biimidazole and malonate ligands. Additionally, coordination of the carboxylate group with the metallic centre helps sustain remarkable supramolecular assemblies, such as layers, helices, double helix columns or 3D channeled architectures, including mixed-metal complexes, into a single structure.
本文介绍了基于分子[Cu(2,2'-联咪唑)]模块和丙二酸根阴离子自组装形成的四种新型超分子氢键排列的合成及结构表征，即四(2,2'-联咪唑)二-μ-氯代-二丙二酸根三铜(II)五水合物，[Cu(CHO)Cl(CHN)]·5HO或[Cu(Hbiim)(μ-Cl)Cu(mal)]·5HO，水合(2,2'-联咪唑)丙二酸根铜(II)二水合物，[Cu(CHO)(CHN)(HO)]·2HO或[Cu(Hbiim)(mal)(HO)]·2HO，双[水合双(2,2'-联咪唑)铜(II)]二丙二酸根二高氯酸根铜(II) 2.2水合物，[Cu(CHN)(HO)][Cu(CHO)(ClO)]·2.2HO或[Cu(Hbiim)(HO)][Cu(mal)(ClO)]·2.2HO，以及双(2,2'-联咪唑)铜(II)双[双(2,2'-联咪唑)(2-羧基乙酸根)丙二酸根铜(II)]十三水合物，[Cu(CHN)][Cu(CHO)(CHO)(CHN)]·13HO或[Cu(Hbiim)][Cu(Hbiim)(Hmal)(mal)]·13HO。这些组装体的特征是互补的供体-受体分子相互作用，显示出配位的2,2'-联咪唑和丙二酸根配体的羧酸根、羧酸和N-H基团之间反复出现且独特的氢键偏好模式。此外，羧酸根与金属中心的配位有助于将显著的超分子组装体，如层、螺旋、双螺旋柱或三维通道结构，包括混合金属配合物，维持在单一结构中。
