Guest-induced assembly of tetracarboxyl-cavitand and tetra(3-pyridyl)-cavitand into a heterodimeric capsule via hydrogen bonds and CH-halogen and/or CH-π interaction:: Control of the orientation of the encapsulated guest
Guest-induced assembly of tetracarboxyl-cavitand and tetra(3-pyridyl)-cavitand into a heterodimeric capsule via hydrogen bonds and CH-halogen and/or CH-π interaction:: Control of the orientation of the encapsulated guest
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DOI：
10.1021/ja035337q
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发表时间：
2003-09-03
影响因子：
15
通讯作者：
Yamaguchi, K
中科院分区：
文献类型：
--
作者：
Kobayashi, K;Ishii, K;Yamaguchi, K
四羧基空腔体1和四（3-吡啶基）空腔体2在来宾或溶剂诱导下组装成异二聚体胶囊1。通过四个分子间的CO2H…研究了氮氢键在溶液和固体中的作用。在H-1核磁共振研究中，CDCl3中1a和2a (R = (CH2)(6)CH3)的1:1混合物产生了各种复杂聚集体的混合物，而CDCl2CDCl2或对二甲苯-d（10）中的这种混合物只产生异二聚体胶囊1a(.)2a。发现合适的1,4-二取代苯是诱导1a（）排他性形成的合适客体。CDCl3中的2a。客人诱导形成客人包封异二聚体胶囊的能力，客人@（1a）。2a)，按顺序增加对乙基甲苯< 1-乙基-4-甲氧基苯小于或等于1-乙基-4-碘苯小于或等于1,4-二溴苯< 1-碘-4-甲氧基苯小于或等于1,4-二甲氧基苯小于或等于1,4-二碘苯。H-1核磁共振研究表明，在1,4-二卤苯和1,4-二甲氧基苯的甲氧基质子和1,4-二甲氧基苯的芳香腔之间的CH-pi相互作用和1,4-二卤苯@ （1a(.)2a）和1,4-二甲氧基苯@ （1a(.)2a）的形成过程中起着重要作用。2),分别。guest @ （1b）的单晶x射线衍射初步分析2b) (R = (CH2)(2)-Ph；Guest = 1-碘-4-甲氧基苯或对二甲苯)确认Guest封装在1b（。）2b与来宾的长轴沿1b的长轴（。）发现包封的1-碘-4-甲氧基的碘和甲氧基分别相对于2b和1b单元的空腔定向。
The guest- or solvent-induced assembly of a tetracarboxyl-cavitand 1 and a tetra(3-pyridyl)-cavitand 2 into a heterodimeric capsule 1(.)2 in a rim-to-rim fashion via four intermolecular CO2H...N hydrogen bonds has been investigated both in solution and in the solid state. In the H-1 NMR study, a 1:1 mixture of 1a and 2a (R = (CH2)(6)CH3) in CDCl3 gave a mixture of various complicated aggregates, whereas this mixture in CDCl2CDCl2 or p-xylene-d(10) exclusively produced the heterodimeric capsule 1a(.)2a. It was found that an appropriate 1,4-disubstituted-benzene is a suitable guest for inducing the exclusive formation of 1a(.)2a in CDCl3. The ability of a guest to induce the formation of guest-encapsulating heterodimeric capsule, guest@(1a(.)2a), increased in the order p-ethyltoluene < 1-ethyl-4-methoxybenzene less than or equal to 1-ethyl-4-iodobenzene less than or equal to 1,4-dibromobenzene < 1-iodo-4-methoxybenzene less than or equal to 1,4-dimethoxybenzene less than or equal to 1,4-diiodobenzene. The H-1 NMR study revealed that a CH-halogen interaction between the inner protons of the methylene-bridge rims (-O-HoutCHin-O-) of the 1a and 2a units and the halogen atoms of 1,4-dihalobenzenes and a CH-pi interaction between the methoxy protons of 1,4-dimethoxybenzene and the aromatic cavities of the 1 a and 2a units play important roles in the formation of 1,4-dihalobenzene @ (1a(.)2a) and 1,4-dimethoxybenzene @ (1a(.)2a), respectively. A preliminary single-crystal X-ray diffraction analysis of guest @ (1b(.)2b) (R = (CH2)(2)-Ph; guest = 1-iodo-4-methoxybenzene or p-xylene) confirmed that the guest encapsulated in 1b(.)2b is oriented with the long axis of the guest along the long axis of 1b(.)2b and that the iodo and the methoxy groups of the encapsulated 1-iodo-4-methoxybenzene are specifically oriented with respect to the cavities of the 2b and 1b units, respectively.