Gross Dustin E, Mikkilineni Vinay, Lynch Vincent M, Sessler Jonathan L
Department of Chemistry and Biochemistry, Institute for Cellular and Molecular Biology, 1 University Station-A5300, The University of Texas, Austin, Texas 78712-0165, USA.
Supramol Chem. 2010 Feb 1;22(2):135. doi: 10.1080/10610270903304434.
A new set of diamide receptors containing anthracene and carbazole bridging subunits and either pyrrole or phenyl substituents were synthesized. The four systems produced in this way were shown to bind representative anions in DMSO-d(6) solution and in the solid state. A higher relative affinity for two test oxoanions, namely dihydrogen phosphate and benzoate, over chloride anion was seen in solution, with the anions in question being studied in the form of their respective tetrabutylammonium salts. However, the specifics of the anion recognition process were seen to depend on structure, with the pyrrole-containing systems displaying higher relative affinities than their corresponding phenyl-containing congeners, and the carbazole receptors proving more effective than the anthracene analogues. Such observations provide support for the notion that both the carbazole NH and the pyrrolic NH protons play an important role in stabilizing the receptor-bound anions in solution. Structural analyses of several anion complexes of the diamidopyrrole carbazole receptor reveal that this is not necessarily the case in the solid state; specifically, the pyrrole NH protons are seen to interact with the amide oxygen of another molecule. The net result is an extended a one-dimensional coordinaton polymer.
合成了一组新的含蒽和咔唑桥连亚基以及吡咯或苯基取代基的二酰胺受体。结果表明，以这种方式制备的四种体系在氘代二甲亚砜（DMSO-d(6)）溶液和固态中均能结合代表性阴离子。在溶液中观察到，相对于氯离子，这四种体系对两种测试含氧阴离子（即磷酸二氢根和苯甲酸根）具有更高的相对亲和力，所研究的阴离子以其各自的四丁基铵盐形式存在。然而，阴离子识别过程的具体情况取决于结构，含吡咯的体系比其相应的含苯基同系物表现出更高的相对亲和力，咔唑受体比蒽类似物更有效。这些观察结果支持了咔唑NH和吡咯NH质子在溶液中稳定受体结合阴离子方面都起重要作用这一观点。对二酰胺吡咯咔唑受体的几种阴离子配合物的结构分析表明，在固态中情况未必如此；具体而言，吡咯NH质子与另一个分子的酰胺氧相互作用。最终结果是形成了一种延伸的一维配位聚合物。
