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2:2 Complexes from Diphenylpyridiniums and Cucurbit[8]uril: Encapsulation‐Promoted Dimerization of Electrostatically Repulsing Pyridiniums
Chemistry - An Asian Journal ( IF 3.5 ) Pub Date : 2018-04-25 , DOI: 10.1002/asia.201701816 Bo Yang 1 , Shang-Bo Yu 1 , Hui Wang 1 , Dan-Wei Zhang 1 , Zhan-Ting Li 1
Chemistry - An Asian Journal ( IF 3.5 ) Pub Date : 2018-04-25 , DOI: 10.1002/asia.201701816 Bo Yang 1 , Shang-Bo Yu 1 , Hui Wang 1 , Dan-Wei Zhang 1 , Zhan-Ting Li 1
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Rigid linear compounds G1 and G2, which contained two 4‐phenylpyridinium (PhPy+) units, have been prepared to investigate their binding with cucurbit[8]uril (CB[8]). X‐ray crystallographic structures revealed that in the solid state both compounds were included by CB[8], through antiparallel stacking, to form 2:2 quaternary complexes (G1)2@(CB[8])2 and (G2)2@(CB[8])2. For the former complex, CB[8] entrapped G1 by holding two heterodimers of its Py+ and benzyl units, which were at opposite ends of the backbone. In contrast, for the first time, the second complex disclosed parallel stacking of two cationic Py+ units of G2 in the cavity of CB[8] in the solid state, despite the generation of important electrostatic repulsion. Isothermal titrations in water afforded high apparent association constants of 4.36×106 and 6.43×106 m−1 for 1:1 complexes G1@CB[8] and G2@CB[8], respectively, and 1H NMR spectroscopy experiments in D2O confirmed a similar stacking pattern to that observed in the solid state. A previous study and crystal structures of the 2:1 complexes formed between three new controls, G3–5, and CB[8] did not display such unusual stacking of the cationic Py+ unit; this may be attributed to the multivalency of the two CB[8] encapsulation interactions.
中文翻译：
2：2来自二苯基吡啶鎓和葫芦[8] uril的复合物：静电排斥吡啶的包封促进的二聚。
刚性线性化合物G1和G2含有两个4-苯基吡啶（PhPy +）单元，已经准备好研究它们与葫芦丝[8] uril（CB [8]）的结合。X射线晶体学结构表明，在固态下，CB [8]通过反平行堆积将这两种化合物包括在内，形成2：2季铵盐配合物（G1）2 @（CB [8]）2和（G2）2 @ （CB [8]）2。对于前一个复合物，CB [8]通过持有其Py +的两个异二聚体来捕获G1。和苄基单元，它们在主链的相对端。相反，第二种复合物首次公开了在固态下CB [8]腔中G2的两个阳离子Py +单元的平行堆叠，尽管产生了重要的静电排斥力。水中等温滴定分别为1：1配合物G1 @CB [8]和G2 @CB [8]提供了4.36×10 6和6.43×10 6 m -1的高表观缔合常数，并在1 H NMR光谱实验中第2天 O证实了与固态观察到的堆积模式相似的堆积模式。先前的研究和在三个新的对照G3–5和CB [8]之间形成的2：1配合物的晶体结构没有显示出阳离子Py +单元的这种异常堆积。这可能归因于两个CB [8]封装交互作用的多价。
更新日期：2018-04-25
中文翻译：
2：2来自二苯基吡啶鎓和葫芦[8] uril的复合物：静电排斥吡啶的包封促进的二聚。
刚性线性化合物G1和G2含有两个4-苯基吡啶（PhPy +）单元，已经准备好研究它们与葫芦丝[8] uril（CB [8]）的结合。X射线晶体学结构表明，在固态下，CB [8]通过反平行堆积将这两种化合物包括在内，形成2：2季铵盐配合物（G1）2 @（CB [8]）2和（G2）2 @ （CB [8]）2。对于前一个复合物，CB [8]通过持有其Py +的两个异二聚体来捕获G1。和苄基单元，它们在主链的相对端。相反，第二种复合物首次公开了在固态下CB [8]腔中G2的两个阳离子Py +单元的平行堆叠，尽管产生了重要的静电排斥力。水中等温滴定分别为1：1配合物G1 @CB [8]和G2 @CB [8]提供了4.36×10 6和6.43×10 6 m -1的高表观缔合常数，并在1 H NMR光谱实验中第2天 O证实了与固态观察到的堆积模式相似的堆积模式。先前的研究和在三个新的对照G3–5和CB [8]之间形成的2：1配合物的晶体结构没有显示出阳离子Py +单元的这种异常堆积。这可能归因于两个CB [8]封装交互作用的多价。
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