六元瓜环、对称四甲基六元瓜环与2,2'-(1,8-辛烷)-二异喹啉二溴化物的自组装模式

doi:10.7503/cjcu20140035

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (8): 1697.doi: 10.7503/cjcu20140035

六元瓜环、对称四甲基六元瓜环与2,2'-(1,8-辛烷)-二异喹啉二溴化物的自组装模式

范志芳^1,², 薛赛凤²(), 陶朱²

1. 六盘水师范学院化学与化学工程系, 六盘水 550003
2. 贵州大学贵州省大环化学及超分子化学重点实验室, 贵阳 550025

收稿日期:2014-01-13 出版日期:2014-08-10 发布日期:2014-03-31
作者简介:联系人简介: 薛赛凤, 女, 教授, 博士生导师, 主要从事超分子化学研究. E-mail: sfxue@gzu.edu.cn
基金资助:
国家自然科学基金(批准号: 20972034)、贵州省教育厅自然科学研究项目(批准号: 黔省专合字[2009]103号)和煤系固体废弃物资源化利用实验室项目[批准号: (2011)278]资助

Supramolecular Assemblies of Cucurbit[6]uril and Symmetrical Tetramethyl-substituted Cucurbit[6]uril with Bromide Salt of 2,2'-(Hexane-1,8-diyl)diisoquinolinium^†

FAN Zhifang^1,², XUE Saifeng^2,^*(), TAO Zhu²

1. Department of Chemistry and Chemical Engineering, Liupanshui Normal College, Liupanshui 553004, China
2. Key Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, Guizhou University, Guiyang 550025, China

Received:2014-01-13 Online:2014-08-10 Published:2014-03-31
Contact: XUE Saifeng E-mail:sfxue@gzu.edu.cn
Supported by:
Support by the National Natural Science Foundation of China(No.20972034), the Natural Science Research Project of the Education Department of Guizhou Province of China(No [2009]103) and the Solid Waste Recycling Laboratory of Coal Utilization China[No (2011)-278]

摘要/Abstract

摘要：

利用核磁共振波谱、紫外吸收光谱、荧光光谱和单晶X射线衍射分析等考察了六元瓜环(Q[6])及对称四甲基六元瓜环(TMeQ[6])与2,2'-(1,8-辛烷)-二异喹啉二溴化物的相互作用. 实验结果表明, 客体分子分别与这2种瓜环自组装形成相似的1∶1包结配合物, 但晶体结构分析结果表明两个体系在主客体分子间作用力诱导下形成了不同的空间堆积模式, 其包结常数分别为K_K8-Q[6]=4.18×10⁷ L/mol, K_K8-TMeQ[6]=6.11×10⁷ L/mol.

关键词: 对称四甲基六元瓜环, 六元瓜环, 2, 2'-(辛烷)-二异喹啉二溴化物, 超分子自组装

Abstract:

Interactions between cucurbit[6]uril(Q[6]) or symmetrical tetramethyl-substituted cucurbit[6]uril(TMeQ[6]) and bromide salt 2,2'-(hexane-1,8-diyl)diisoquinolinium were studied experimentally by ¹H NMR technology, electronic absorption spectroscopy, fluorescence spectroscopy and single crystal X-ray diffraction method. The experimental results revealed that the interaction of the guest molecule with both Q[6]s respectively could form the similarity inclusion complexes with host/guest ratio of 1∶1 in solution state, the binding constants(K) of the two complexes were in 10⁷ scale. While the crystal structures from two systems showed different supramolecular assemblies due to the geometrical difference from two Q[6]s. The study showed that a 3D framework can be induced by the π-π stacking of the protruded isoquinolyl moieties. It may provide information in designment of molecular channel, machines and switches.

Key words: Symmetrical tetramethyl-substituted cucurbit[6]uril, Cucurbit[6]uril, Bromide salt of 2, 2'-(hexane-1, 8-diyl) diisoquinolinium, Supramolecular assembly

中图分类号:

O625

TrendMD:

范志芳, 薛赛凤, 陶朱. 六元瓜环、对称四甲基六元瓜环与2,2'-(1,8-辛烷)-二异喹啉二溴化物的自组装模式. 高等学校化学学报, 2014, 35(8): 1697.

FAN Zhifang, XUE Saifeng, TAO Zhu. Supramolecular Assemblies of Cucurbit[6]uril and Symmetrical Tetramethyl-substituted Cucurbit[6]uril with Bromide Salt of 2,2'-(Hexane-1,8-diyl)diisoquinolinium^†. Chem. J. Chinese Universities, 2014, 35(8): 1697.

图/表 6

Fig.1 Structures of the host and the guest used in this work

Table 1 Crystallographic data, collection conditions and refinement parameters for the mentioned compounds

Complex	K8@Q[6]	K8@TMeQ[6]	V/nm³	2.0055(5)	15.0735
Empirical formula	C₆₂H₁₀₂N₂₆O₃₄S	C₄₀H₄₅N₂₄O₁₂BrCl	Z	2	8
CCDC No.	732231	952022	$D calcd .$ /(g·cm^-3)	1.45	1.517
Formula weight	925.78	1721.12	F(000)	944	7040
Crystal system	Triclinic	Monoclinic	M_u	0.146	0.136
Space group	P $1 ˉ$	C2/c	T/K	273(2)	273(2)
a/nm	1.28486(19)	4.598	Unique reflns	6771	11380
b/nm	1.32895(19)	1.4251	Obsd reflns	4850	5781
c/nm	1.32895(19)	3.2411	Params	585	1056
α/(°)	109.10	90.00	R[I >2σ(I)]	0.0877	0.2280
β/(°)	101.844(4)	134.785	wR[I >2σ(I)]	0.2621	0.4728
γ/(°)	101.844(4)	90.00

Table 1 Crystallographic data, collection conditions and refinement parameters for the mentioned compounds

Complex	K8@Q[6]	K8@TMeQ[6]	V/nm³	2.0055(5)	15.0735
Empirical formula	C₆₂H₁₀₂N₂₆O₃₄S	C₄₀H₄₅N₂₄O₁₂BrCl	Z	2	8
CCDC No.	732231	952022	$D calcd .$ /(g·cm^-3)	1.45	1.517
Formula weight	925.78	1721.12	F(000)	944	7040
Crystal system	Triclinic	Monoclinic	M_u	0.146	0.136
Space group	P $1 ˉ$	C2/c	T/K	273(2)	273(2)
a/nm	1.28486(19)	4.598	Unique reflns	6771	11380
b/nm	1.32895(19)	1.4251	Obsd reflns	4850	5781
c/nm	1.32895(19)	3.2411	Params	585	1056
α/(°)	109.10	90.00	R[I >2σ(I)]	0.0877	0.2280
β/(°)	101.844(4)	134.785	wR[I >2σ(I)]	0.2621	0.4728
γ/(°)	101.844(4)	90.00

Fig.2 Different stacking models of crystal structure of K8@Q[6] pseudorotaxane (A) K8@Q[6] pseudorotaxane and the two different 1D assembled chains formed; (B) by π-π stacking; (C) by hydrogen bonding; (D) 2D network consisting of hosts with the guests omitted; (E) network of K8@Q[6] pseudorotaxanes. All the hydrogen, Br atoms and some water molecules are omitted for clarity.

Fig.3 Different stacking models of crystal structure of K8@TMeQ[6] pseudorotaxane (A) K8@TMeQ[6] pseudorotaxane; (B) basic π-π stacks of the neighboring protruded isoquinolyl moieties of K8@TMeQ[6] pseudorotaxane(top view); (C) 3D framework consisting of K8@TMeQ[6] pseudorotaxanes(top view); (D) side view of the grid containing the stacked isoquinolyl moieties; (E) side view of the grid contains chloride anions and water molecules. All hydrogen atoms and some water molecules are omitted for clarity.

Fig.4 UV spectra(A, C) and fluorescence emission spectra(B, D) of K8@Q[6](A, B) and K8@TMeQ[6](C, D) systems

Fig.5 Plots of UV spectra(A, C) and fluorescence emission spectra(B, D) of K8@Q[6](A, B) and K8@TMeQ[6](C, D) systems corresponding to Fig.4 Electronic absorption spectra and fluorescence emissionspectra of the guest K8 in the presence of increasing concentrations of Q[6] and TMeQ[6] aqueous solution. (A) A vs. n(Q[6])/n(K8) curve; inset of (A) ΔA vs. n(K8)/[n(Q[6])+n(K8)]; (B) If vs. n(Q[6])/n(K8) curve; inset of (B) ΔIf vs. n(K8)/[n(Q[6])+n(K8)]; (C) A vs. n(TMeQ[6])/n(K8); inset of (C) ΔA vs. n(K8)/[n(TMeQ[6])+n(K8)] at λmax; (D) If vs. n(TMeQ[6])/n(K8); inset of (D) ΔIf vs. n(K8)/[n(TMeQ[6])+n(K8)] at λmax.

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六元瓜环、对称四甲基六元瓜环与2,2'-(1,8-辛烷)-二异喹啉二溴化物的自组装模式

Supramolecular Assemblies of Cucurbit[6]uril and Symmetrical Tetramethyl-substituted Cucurbit[6]uril with Bromide Salt of 2,2'-(Hexane-1,8-diyl)diisoquinolinium^†

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