Supramolecular Self-assembly of Symmetric Dicyclohexanocucurbit[6]uril and Nicotinic Hydrazide

doi:10.6023/A21100465

Abstract

Cucurbit[n]uril (Q[n]) is a relatively new supramolecular macrocyclic compound, which has a unique structure comprised of a hydrophobic cavity with intermediate potential, two carbonyl portals with negative potential, and an outer surface with positive potential. Cyclohexyl-substituted Q[n]s have also attracted a lot of attention as the first member of the Q[n] family that can be dissolved in organic solvents and water. In this paper, the interaction modes between the symmetric dicyclohexanocucurbit[6]uril (CyH₂Q[6]) as a host and nicotinic hydrazide (NH) as a guest were investigated by nuclear magnetic resonance spectroscopy (¹H NMR), isothermal titration calorimetry (ITC), matrix assisted laser desorption ionization time of flight (MALDI-TOF) mass spectrometry, and single-crystal X-ray diffraction. The ¹H NMR spectrum results showed that the proton peaks shift to the downfield, indicating that NH is located at the portal of CyH₂Q[6]. ITC experiment results showed that the binding constant (K_a) of NH@CyH₂Q[6] is (1.019±0.118)×10³ L•mol^-1, the host-guest binding ratio is 0.954±0.013, and the enthalpy value is ΔH=(–48.21±0.35) kJ•mol^-1 and entropy value TΔS=(–31.04±0.52) kJ•mol^-1. The MALDI-TOF mass spectrum also showed that the molecular ion peak m/z is 1242.4542 (theoretical value: 1242.1603), which is attributed to [CyH₂Q[6]•HNH]⁺. These experimental results showed that CyH₂Q[6] formed a stable 1∶1 exclusion complex with NH in an aqueous solution. In addition, the host CyH₂Q[6], ZnCl₂ and the guest NH were added to HCl aqueous solution, and the complex single-crystal structure was obtained by evaporation and standing. The single-crystal structure of the complex showed that there are ion-dipole interactions and hydrogen bonds between the carbonyl oxygen of CyH₂Q[6] and NH, and there are ion-dipole interactions between the outer surface of CyH₂Q[6] and [ZnCl₄]^2-. These weak interactions are the driving forces of the multi-dimensional and multi-level supramolecular framework formed by the complex.

Key words: symmetric dicyclohexanocucurbit[6]uril, nicotinic hydrazide, complex, supramolecular framework, self-assembly

Cite this article

Yanmei Jin, Ye Meng, Yuan Li, Jianhua Shi, Lei Deng. Supramolecular Self-assembly of Symmetric Dicyclohexanocucurbit[6]uril and Nicotinic Hydrazide[J]. Acta Chimica Sinica, 2022, 80(1): 44-48.

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Experiment	NH@CyH₂Q[6]
Model	Independent
K_a/(L•mol^-1)	(1.019±0.118)×10³
ΔH/(kJ•mol^-1)	–48.21±0.35
n	0.954±0.013
TΔS/(kJ•mol^-1)	–31.04±0.52

Experiment	NH@CyH₂Q[6]
Model	Independent
K_a/(L•mol^-1)	(1.019±0.118)×10³
ΔH/(kJ•mol^-1)	–48.21±0.35
n	0.954±0.013
TΔS/(kJ•mol^-1)	–31.04±0.52

NH@CyH₂Q[6]
Bond	Length/nm	Bond	Length/nm
N15―O3	0.2841	N13―O5	0.2680
N15―O6	0.2925	N13―O6	0.3009
N15―O2	0.2927	C22―O6	0.2953
N14―O1	0.2990	C10―Cl1	0.3318
N14―O4	0.3048	H13A―Cl6	0.2739
C24―O1	0.3095	H5―Cl3	0.2950
C24―O4	0.3035	H1A―Cl3	0.2782
C27―O5	0.3162	H1B―Cl2	0.2924

NH@CyH₂Q[6]
Bond	Length/nm	Bond	Length/nm
N15―O3	0.2841	N13―O5	0.2680
N15―O6	0.2925	N13―O6	0.3009
N15―O2	0.2927	C22―O6	0.2953
N14―O1	0.2990	C10―Cl1	0.3318
N14―O4	0.3048	H13A―Cl6	0.2739
C24―O1	0.3095	H5―Cl3	0.2950
C24―O4	0.3035	H1A―Cl3	0.2782
C27―O5	0.3162	H1B―Cl2	0.2924

NH@CYH₂Q[6]
Empirical formula	C₅₆H₆₆Zn₂Cl₈N₃₀O₁₄	Formula weight	1797.72
Crystal system	Triclinic	Space group	P-1
a/nm	1.2304(3)	b/nm	1.3677(3)
c/nm	1.3896(4)	α/(°)	71.692(9)
β/(°)	76.013(7)	γ/(°)	67.789(7)
V/nm³	2.0352(9)	Z	1
D_calcd/(g•cm^-3)]	1.467	T/K	298
μ/mm^-1	0.927	Parameters	525
R_int	0.0994	R[I>2σ(I)]^a	0.1458
wR[I>2σ(I)]^b	0.3933	R (all data)	0.2284
wR (all data)	0.4437	GOF on F²	1.352

对称二环己基取代六元瓜环与3-吡啶甲酰肼的超分子自组装