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首页> 外文期刊>Chemistry: A European journal >Tetra- and Octalactam Macrocycles and Catenanes with Exocyclic Metal Coordination Sites: Versatile Building Blocks for Supramolecular Chemistry
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Tetra- and Octalactam Macrocycles and Catenanes with Exocyclic Metal Coordination Sites: Versatile Building Blocks for Supramolecular Chemistry

机译：具有外环金属配位位点的四-和八-内酰胺大环和连环化合物：超分子化学的多功能构建基块

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摘要

The synthesis of a new tetra-lactam macrocycle and the simultaneous formation of catenanes and larger octalactam macrocycles is reported. These species bear 2,2'-biquinoline moieties suitably positioned to bind a metal center at the outer periphery of th emacrocycles. ~1h nmr Chemical shifts permit the unambiguous distinction of transoid and cisoid conformations of the biquinoline moiety, thereby allowing an unequivocal identification of the catenane and octalactam structures, despite the fact that both have the same elemental composition and bear identical structural subunits. With the aid of an anion template effect, rotaxanes can be prepared from the smaller tetralactam macrocycle. These reveal significantly altered requirements in terms of the stopper size as compared to previously reported tetralactam wheels. Several copper(I)-mediated dimers and a (bpy)_2Ru~II complex (bpy=2,2'-bipyridine) have been synthesized from the tetralactam macrocycle and the rotaxanes. The anion binding abilities of hte tetralactam macrocycle and its (bpy)_2Ru~II complex in DMSO have been compared by ~1H NMR titration experimentas, which revealed significantly enhanced binding by the metal complex. Mass spectrometry has been used to study the potential formation of larger assemblies of copper(I) and the catenane built-up from two tetralactam mafrocycles. Indeed, a 2:2 complex was identified. In contrast, the octalactam macrocycle of the same elemental composition yields only 1:1 complexes, with the Cu~I ion connecting its two biquinoline moieties in the center of a figure-eight-shaped molecule. Molecular modeling studies support the structural assignments made.
机译：报道了新的四-内酰胺大环的合成以及同时形成链烷和更大的八内酰胺大环的形成。这些物质带有2,2'-联喹啉部分，它们的位置合适，可以与大环外缘的金属中心结合。 〜1h nmr化学位移可以清楚地区分联喹啉部分的反式和顺式构象，从而可以明确鉴定联烷和八内酰胺结构，尽管事实是它们的元素组成相同且具有相同的结构亚基。借助于阴离子模板作用，可以从较小的四内酰胺大环化合物制备轮烷。与先前报道的四内酰胺车轮相比，这些揭示了在塞子尺寸方面的显着改变的要求。从四内酰胺大环和轮烷合成了几种铜（I）介导的二聚体和（bpy）_2Ru〜II配合物（bpy = 2,2'-联吡啶）。 〜1H NMR滴定实验比较了四内酰胺大环及其（bpy）_2Ru〜II配合物在DMSO中的阴离子结合能力，结果表明金属配合物的结合显着增强。质谱已用于研究较大的铜（I）组装体的潜在形成和由两个四内酰胺大环环氧化物形成的链烷的形成。实际上，已确定了2：2复杂度。相反，相同元素组成的八内酰胺大环仅产生1：1的络合物，Cu〜I离子将其两个联喹啉部分连接在一个八字形分子的中心。分子建模研究支持所做的结构任务。

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