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

doi:10.7503/cjcu20140035

Abstract

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

CLC Number:

O625

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2014, 35(8): 1697.

Figures/Tables 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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