Assembly and Property of Rotaxane Based on Cucurbit[6, 7]urils Host and Two Kinds of N,N'-Phthalimide Appended 4,4'-Dipyridyl Terminated Viologen Guest†

doi:10.7503/cjcu20150438

Abstract

Abstract:

Two guests based on N,N'-phthalimide substituted 4,4'-dipyridyl with different alkyl chain lengths were synthesized(G1 and G2). The supramolecular self-assemblies of G1 and G2 with cucurbit[6]uril(Q[6]) and cucurbit[7]uril(Q[7]) were evaluated by UV-Vis spectra, hydrogen nuclear magnetic resonance(¹H NMR) and isothermal titration calorimetry(ITC). The experiment results suggested that [2]rotaxane can be only formed between G1 and Q[6] in boiling aqueous solution by slipping. On the contrary, [2]pseudorotaxane can be easily formed between Q[7] and G1 or G2 in aqueous solution at room temperature.

Key words: Cucurbituril, Rotaxane, Viologen, Phthalimide

CLC Number:

TrendMD:

CHEN Shiyan, CUI Xiaowei, WANG Chuanzeng, NI Xinlong, MA Peihua, ZHANG Jianxin. Assembly and Property of Rotaxane Based on Cucurbit[6, 7]urils Host and Two Kinds of N,N'-Phthalimide Appended 4,4'-Dipyridyl Terminated Viologen Guest^†[J]. Chem. J. Chinese Universities, 2015, 36(10): 1919.

Figures/Tables 6

Synthesis of 1,1'-dimethylphthalimide-4,4'-bipyridium dibromide(G1) and 1,1'-dibutylphthalimide-4,4'-bipyridium dibromide(G2)

Fig.1 UV-Vis absorption spectra of G1(A) and G2(B) upon addition of increasing concentrations of Q[7](3.0×10-5 mol/L for G1 and 2.0×10-5 mol/L for G2) in waterInsets: relationship of A and n(Q[7])∶n(G1or G2) at 260 nm.

Fig.2 Correeted heat rate(A, B) and normalized fit(C, D) for the complexation of Q[7]-G1(A, C) and Q[7]-G2(B, D)

Table 1 Thermodynamic binding data for Q[7]-G1 and Q[7]-G2

Host-Guest	K_a/(L·mol^-1)	ΔG/(kJ·mol^-1)	ΔH/(kJ·mol^-1)	TΔS/(kJ·mol^-1)
Q[7]-G1	(2.171±0.07)×10⁵	-30.46±0.07	-35.81±0.03	-5.352±0.04
Q[7]-G2	(3.995±0.08)×10⁶	-37.68±0.06	-29.33±0.03	8.351±0.03

Fig.3 1H NMR spectra of G1(2.0 mmol/L)(a) and G1 in the presence of 1.0(b), 2.0(c) and 3.0 mmol/L(d) of Q[7] in D2O

Fig.4 1H NMR spectra of G2(2.0 mmol/L)(a) and G2 in the presence of 1.0(b), 2.0(c) and 3.0 mmol/L(d) of Q[7] in D2O

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