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beta,beta-(1,4-Dithiino)subporphyrin Dimers Capturing Fullerenes with Large Association Constants

机译:β,β-(1,4-二硫代)亚卟啉二聚体捕获具有大缔合常数的富勒烯

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摘要

beta,beta-(1,4-Dithiino)subporphyrin dimers 7-syn and 7-anti were synthesized by the nucleophilic aromatic substitution reaction of 2-bromo-3-(4-methoxyphenylsulfonyl)subporphyrin 4 with 2,3-dimercaptosubporphyrin 5 under basic conditions followed by axial arylation. Additions of C-60 or C-70 to a dilute solution of 7-anti (ca. 10(-6) M) in toluene did not cause appreciable UV/Vis spectral changes, while similar additions to a concentrated solution (ca. 10(-3)M) resulted in precipitation of complexes. In contrast, dimer 7-syn captured C-60 and C-70 in different complexation stoichiometries in toluene; a 1:1 manner and a 2:1 manner, respectively, with large association constants; K-a=(1.9 +/- 0.2) x 10(6) M-1 for C-60@7-syn, and K-1=(1.6 +/- 0.5) x 10(6) and K-2=(1.8 +/- 0.9) x 10(5) M-1 for C-70@(7-syn)(2). These association constants are the largest for fullerenes-capture by bowl-shaped molecules reported so far. The structures of C-60@7-anti, C-70@7-anti, C-60@7-syn, and C-70@7-syn have been determined by single-crystal X-ray diffraction analysis.
机译:通过2-溴-3-(4-甲氧基苯基磺酰基)亚卟啉4与2,3-二巯基亚卟啉5的亲核取代反应,合成了β,β-(1,4-二硫代)亚卟啉二聚体7-syn和7-anti。基本条件,然后进行轴向芳基化。将C-60或C-70添加到7-anti(ca. 10(-6)M)的甲苯稀释溶液中不会引起明显的UV / Vis光谱变化,而将类似的添加物添加到浓溶液中(大约10 (-3)M)导致络合物沉淀。相反,二聚体7-syn在甲苯中以不同的络合化学计量比捕获了C-60和C-70。具有较大关联常数的1:1方式和2:1方式;对于C-60 @ 7-syn,Ka =(1.9 +/- 0.2)x 10(6)M-1,而K-1 =(1.6 +/- 0.5)x 10(6)和K-2 =(1.8 +/- 0.9)x 10(5)M-1,用于C-70 @(7-syn)(2)。这些结合常数是迄今为止报道的碗状分子捕获富勒烯的最大关联常数。 C-60 @ 7-anti,C-70 @ 7-anti,C-60 @ 7-syn和C-70 @ 7-syn的结构已通过单晶X射线衍射分析确定。

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