From 2-Fold Completive to Integrative Self-Sorting: A Five-Component Supramolecular Trapezoid
From 2-Fold Completive to Integrative Self-Sorting: A Five-Component Supramolecular Trapezoid
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DOI：
10.1021/ja907185k
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发表时间：
2009-11-18
影响因子：
15
通讯作者：
Schmittel, Michael
中科院分区：
文献类型：
--
作者：
Mahata, Kingsuk;Schmittel, Michael
将两个不完整的自我分类过程合并成一个过程，从而定量地利用图书馆的所有成员，这一过程可用两次完全自我分类来描述。为了实现这一目标，通过筛选各种因素，如空间和电子效应、pi-pi相互作用和金属-离子特异性，对单个金属-配体结合方案进行了优化，以获得高热力学稳定性和最佳选择性。利用优化的异感金属配体结合基序，建立了四种不同配体(1、2、3、4)和两种不同金属离子(锌、铜)的文库，以评估2次完全自排序。在20种不同的组合中，自分类文库最终只得到了两个基本上定量产量的金属-配体配合物。为了证明2次完全自排序在形成纳米结构中的价值，优化的、高选择性的结合基序被实施到三个多官能团配体中。它们在锌和铜离子存在下的综合自分类导致了超分子梯形T的干净形成，这是一种简单但仍未知的超分子结构。动态梯形T由三种不同的配体组成，具有四种不同的供体-受体相互作用。其结构经核磁共振氢谱、电喷雾电离质谱仪和差示脉冲伏安法(DPV)确证，并排除替代结构。
The amalgamation of two incomplete self-sorting processes into a process that makes quantitative use of all members of the library is described by 2-fold completive self-sorting. Toward this goal, individual metal-ligand binding scenarios were optimized for high thermodynamic stability and best selectivity, by screening a variety of factors, such as steric and electronic effects, pi-pi interactions, and metal-ion specifics. Using optimized, heteroleptic metal-ligand binding motifs, a library of four different ligands (1, 2, 3, 4) and two different metal ions (Zn2+, Cu+) was set up to assess 2-fold completive self-sorting. Out of 20 different combinations, the self-sorting library ended up with only two metal-ligand complexes in basically quantitative yield. To demonstrate the value of 2-fold completive self-sorting for the formation of nanostructures, the optimized, highly selective binding motifs were implemented into three polyfunctional ligands. Their integrative self-sorting in the presence of Zn2+ and Cu+ led to the clean formation of the supramolecular trapezoid T, a simple but still unknown supramolecular architecture. The dynamic trapezoid T consists of three different ligands with four different donor-acceptor interactions. Its structure was established by H-1 NMR spectroscopy, electrospray ionization mass spectroscopy, and differential pulse voltammetry (DPV) and by exclusion of alternative structures.