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

doi:10.6023/A21100465

摘要/Abstract

本工作以对称二环己基取代六元瓜环(CyH₂Q[6])为主体分子, 3-吡啶甲酰肼(NH)为客体分子, 利用核磁共振(¹H NMR)、等温滴定量热(ITC)、基质辅助激光解吸电离飞行时间质谱(MALDI-TOF)研究客体分子与瓜环在水溶液中形成的物质的量比为1∶1的稳定配合物; 用X-射线单晶衍射可以观察到客体分子通过离子-偶极和氢键与瓜环端口羰基氧相互作用, 以及基于瓜环外壁正电性与无机阴离子之间形成的配合物, 从而形成多维多层次超分子框架的自组装体.

关键词: 对称二环己基取代六元瓜环, 3-吡啶甲酰肼, 配合物, 超分子框架, 自组装体

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

引用此文

金艳梅, 蒙叶, 李远, 史建华, 邓雷. 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[J]. 化学学报, 2022, 80(1): 44-48.

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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图/表 9

图1. 主体CyH2Q[6]、客体NH及诱导剂[ZnCl4]2-的分子结构式

Figure 1. The molecular structures of the host CyH2Q[6], the guest NH and the inducer [ZnCl4]2-

图2. NH@CyH2Q[6](D2O)的1H NMR谱图: (a) CyH2Q[6]; (b) n(CyH2Q[6])∶n(NH)=0.49∶1.04; (c) 客体NH

Figure 2. 1H NMR spectra of NH@CyH2Q[6](D2O): (a) CyH2Q[6], (b) n(CyH2Q[6])∶n(NH)=0.49∶1.04, and (c) guest NH

图3. NH@CyH2Q[6]在298.15 K溶液(去离子水)中结合的ITC数据

Figure 3. ITC data for the binding of NH with CyH2Q[6] in aqueous solution (deionized water) at 298.15 K

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

表1. 在298.15 K下, ITC测量的NH和CyH2Q[6]相互作用的热力学

Table 1. ITC measurements of the thermodynamics of NH and CyH2Q[6] interactions at 298.15 K

图4. NH@CyH2Q[6]的MALDI-TOF质谱图

Figure 4. MALDI-TOF mass spectrum of NH@CyH2Q[6]

图5. 配合物的晶体图: (a, b) 配合物的不对称单元; (c) CyH2Q[6]与周围[ZnCl4]2-的弱相互作用

Figure 5. Crystal structure of the complex: (a, b) asymmetric unit of the complex; (c) the weak interactions of CyH2Q[6] with [ZnCl4]2-

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

表2. NH@CyH2Q[6]主要的键长(nm)和键角数据(°)

Table 2. Data of main bond lengths (nm) and bond angles (°) of NH@CyH2Q[6]

图6. 配合物堆积图: (a) NH与CyH2Q[6]超分子链; (b, e, f) 配合物的超分子骨架; (c) 超分子层; (d) [ZnCl4]2-与CyH2Q[6]超分子链

Figure 6. Packing diagram of the complex: (a) supramolecular chain of CyH2Q[6] with NH; (b, e, f) supramolecular framework of the complex; (c) supramolecular layer; (d) supramolecular chain of CyH2Q[6] with [ZnCl4]2-

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

表3. 配合物的晶体结构数据

Table 3. Data of crystal structure of the complex

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