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From a monomer to a protein-sized, doughnut-shaped coordination oligomer - The influence of side chains of C-3-symmetric ligands in supramolecular chemistry

机译:从单体到蛋白质大小的甜甜圈形配位低聚物-C-3对称配体的侧链对超分子化学的影响

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Herein we describe the importance of side chains in C-3-symmetric ligands in supramolecular chemistry. The reaction of the new ligand tris(5-bromo-2-methoxybenzylidene)triamino- guanidinium chloride [H3Me3Br3L]Cl (1) with ZnCl2 results in the formation of the monomeric complex (Et3NH)(2)-[(ZnCl2)(3)Me3Br3L] (2), in which the ligand remains in a conformation less favourable for the coordination of metal centres. The use of the related tris(5-bromo-2-hydroxybenzylidene)tri-aminoguanidinium chloride, [H6Br3L]Cl, under similar conditions, results in the formation of two different dimeric compounds (NH4)[{[Zn(NH3)](3)Br3L}(2)-[mu-(OH)}(3)]center dot 1/4MeOH (3) and [Zn[Zn-2(OH2)(3)(NH3)Br3L}(2)] (4), depending on the solvent mixture used. The comparable reaction of the ligand tris-(5-bromo-2-hydroxy-3-methoxybenzylidene)triaminoguanidinium chloride [H-6(OMe)(3)Br3L]Cl (5), leads to the formation of a doughnut-shaped, protein-sized coordination oligomer (Et3NH)(18)[{Zn[Zn2Cl{(OMe)(3)Br3L}](2)](6)-(mu-Cl)(6)(OH2)(6)]center dot xCH(3)CN (6), which comprises six dimeric [Zn-5-{(OMe)(3)Br3L](2)] units. Whereas 3 and 4 decompose in DMSO solution, 6 is surprisingly stable in the same solvent.
机译:在本文中,我们描述了超分子化学中C-3-对称配体中侧链的重要性。新的配体三(5-溴-2-甲氧基亚苄基)三氨基胍氯化物[H3Me3Br3L] Cl(1)与ZnCl2的反应导致单体络合物(Et3NH)(2)-[(ZnCl2)(3 )(Me3Br3L)(2),其中配体的构象不利于金属中心的配位。在相似的条件下,使用相关的三(5-溴-2-羟基亚苄基)三氨基胍氯化物[H6Br3L] Cl会导致形成两种不同的二聚化合物(NH4)[{[Zn(NH3)]( 3)Br3L}(2)-[mu-(OH)}(3)]中心点1 / 4MeOH(3)和[Zn [Zn-2(OH2)(3)(NH3)Br3L}(2)]( 4),取决于所使用的溶剂混合物。配体三-(5-溴-2-羟基-3-羟基-3-甲氧基亚苄基)三氨基胍氯化物[H-6(OMe)(3)Br3L] Cl(5)的可比反应导致形成甜甜圈状,蛋白质大小的配位低聚物(Et3NH)(18)[{Zn [Zn2Cl {(OMe)(3)Br3L}](2)](6)-(mu-Cl)(6)(OH2)(6)]中心点xCH(3)CN(6),它包含六个二聚体[Zn-5-{(OMe)(3)Br3L](2)]单元。尽管3和4在DMSO溶液中分解,但6在相同溶剂中却非常稳定。

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