A dinuclear lanthanide complex for the recognition of bis(carboxylates): Formation of terbium(III) luminescent self-assembly ternary complexes in aqueous solution
A dinuclear lanthanide complex for the recognition of bis(carboxylates): Formation of terbium(III) luminescent self-assembly ternary complexes in aqueous solution
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DOI：
10.1021/ic0614418
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发表时间：
2006-11-13
影响因子：
4.6
通讯作者：
Gunnlaugsson, Thorfinnur
中科院分区：
文献类型：
--
作者：
Harte, Andrew J.;Jensen, Paul;Gunnlaugsson, Thorfinnur
描述了一种配位不饱和阳离子双核铽配合物2中心点Tb-2的合成及其光物理性质，该配合物可以在生理pH下检测缓冲水溶液中单羧酸盐或双羧酸盐的存在。描述了2中心点Na-2的全配体合成和结构表征。光谱测量确定每个Tb（III）金属中心有两个金属结合水分子（q = 2）。对N， N-二甲氨基羧酸4和双（羧酸酯）对苯二甲酸5的识别或感应，也可以作为敏化天线，被发现是通过这些羧酸酯通过位移与金属结合的水分子结合到金属中心而发生的。这导致在溶液中分别以2:1或1:1（离子：2中心点Tb-2）的化学计量形成发光三元配合物。脂肪族双（羧酸）也与2中心点Tb-2结合，其中离子识别和化学计量的选择性由阴离子的结构决定，对苯甲酸最有选择性，6。L-酒石酸或d -酒石酸结合形成三元配合物，具有2:1的化学计量，其中离子识别导致镧系元素发射猝灭。
The synthesis and photophysical properties of a coordinatively unsaturated cationic dinuclear terbium complex, 2 center dot Tb-2, that can detect the presence of mono-or bis(carboxylates) in buffered aqueous solution at physiological pH is described. Full ligand synthesis and structural characterization of 2 center dot Na-2 are also described. Spectroscopic measurements determined that each Tb(III) metal center has two metal-bound water molecules (q = 2). The recognition or sensing of N, N-dimethylaminocarboxylic acid, 4, and the bis(carboxylate) terephthalic acid, 5, which can also function as sensitizing antennae, was found to occur through the binding of these carboxylates to the metal center via the displacement of the metal bound water molecules. This gave rise to the formation of luminescent ternary complexes in solution in 2: 1 or 1: 1 (ion: 2 center dot Tb-2) stoichiometry, respectively. Aliphatic bis(carboxylates) also bind to 2 center dot Tb-2 where the selectivity for the ion recognition and stoichiometry was dictated by the structure of the anion, being most selective for pimelic acid, 6. Binding of either L- or D-tartaric acid gave rise to the formation ternary complex formation, with 2: 1 stoichiometry, where the ion recognition resulted in quenching of the lanthanide emission.