新型杯呋喃大环的合成、结构及其与酸相互作用的研究

doi:10.6023/A25010028

摘要/Abstract

以呋喃和四氢吡喃酮为原料, 在硫酸催化作用下进行缩合反应, 得到杯[4]呋喃大环化合物C4TP和少量杯[6]呋喃大环化合物C6TP. 采用核磁、质谱等分析测试手段对大环进行了表征, 并通过X射线单晶衍射技术测定了大环C4TP和C6TP的晶体结构. 研究发现, 杯呋喃大环C4TP可与酸类化合物发生相互作用而变色, 并通过紫外-可见吸收光谱对大环主体C4TP与系列酸客体的相互作用进行了系统研究. 结果表明, 大环C4TP与不同酸相互作用, 可在可见光区产生新的吸收带而表现出不同颜色, 尤其与甲磺酸(MSA)相互作用时, 可在300~700 nm较宽范围产生吸收而显示绿色. 之后研究了相互作用时间以及加入不同物质的量MSA对可见吸收光谱的影响, 结果显示, 大环分子C4TP与MSA相互作用48 h后, 体系达到稳定状态, 物质的量比为1∶2000时, 相互作用可达到较高强度. 本研究为探索杯呋喃大环与酸类化合物主客体相互作用提供了新的模型和思路.

关键词: 杯呋喃, 大环化合物, 合成, 晶体结构, 主客体相互作用

Calixarene derivatives are widely used in the fields of supramolecular chemistry, coordination chemistry, self-assembly chemistry, optoelectronic materials, and so on. The extensive development of calixarene studies has fostered growing interest in exploring the chemistry of heterocalixarenes, particularly while the aryl units of calixarenes are replaced by heterocycles. Calixfurans, also known as tetraoxaporphyrinogens, represent a significant class of heterocalixarenes. Here, we present a novel class of calixfuran macrocycles and study their interactions with acid compounds. Under catalysis by sulfuric acid, furan and tetrahydro-2H-pyran-4-one were condensed to obtain calix[4]furan macrocyclic compound C4TP and calix[6]furan macrocyclic compound C6TP. The macrocycles were characterized by ¹H nuclear magnetic resonance (¹H NMR), ¹³C nuclear magnetic resonance (¹³C NMR), and mass spectrometry, specifically, the structure of C4TP and C6TP were determined by single-crystal X-ray diffraction analysis. The crystal of C4TP was cuboidal, colorless with smooth surface, good light transmittance, and triclinic system, space group name was P-1. According to the single crystal structure, the molecular skeleton showed a tetragonal cup structure with mirror symmetry. The four furan rings were enclosed like four walls, and tetrahydropyranes were located at the four corners through spiral-conjugate interactions. It was found that the solvents of macrocycle C4TP could change color after interacting with acid compounds. The interactions between the macrocycle host C4TP and a series of acid guests were systematically studied by ultraviolet-visible absorption spectroscopy. The results indicated that the solvents of macrocycle C4TP and different acids presented new absorption bands in the visible light region, exhibiting different colors. Particularly, when macrocycle C4TP was mixed with methanesulfonic acid (MSA), it appeared a wide range absorption over 300~700 nm and displayed green color. Subsequently, we investigated the effects of interaction time and different equivalents of MSA on the ultraviolet-visible absorption spectra. The results figured out that the interaction between the macrocycle C4TP and MSA essentially reached a stable state after 48 h, and achieved a high intensity at a molar ratio of 1∶2000. This study provides a new model and insight into the research of host-guest interactions of calixfuran macrocycles with acid.

Key words: calix[n]furans, macrocyclic compound, synthesis, crystal structure, host-guest interaction

引用此文

王衍军, 王瑞欣, 杨浦曦, 陈慧芷, 郭德复, 高广鹏, 李晓芳. 新型杯呋喃大环的合成、结构及其与酸相互作用的研究[J]. 化学学报, 2025, 83(6): 588-595.

Yanjun Wang, Ruixin Wang, Puxi Yang, Huizhi Chen, Defu Guo, Guangpeng Gao, Xiaofang Li. Research on the Synthesis, Structure and Interactions with Acid of Novel Calixfuran Macrocycle[J]. Acta Chimica Sinica, 2025, 83(6): 588-595.

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图/表 7

图1. 杯呋喃大环C4TP和C6TP的合成路线

Figure 1. Synthetic route of C4TP and C6TP

图2. C4TP的单晶结构, (a)主视图(内插图为晶体光学显微镜晶体图像), (b)俯视图, (c)堆积图

Figure 2. Single crystal structures of C4TP, (a) main view (insert: optical microscopy image), (b) top view and (c) packing mode

图3. C4TP和C6TP的(a)紫外-可见光谱图, (b)循环伏安法电化学图和(c)热重分析图

Figure 3. (a) UV-Vis spectra, (b) cyclic voltammograms (CV) and (c) thermogravimetric analysis (TGA) of C4TP and C6TP

	UV-Vis^a	E_g^opt/ eV	λ_emi^b/ nm	Stokes/ nm	T_d^c/ ℃	CV^d
	λ_max/nm	E_g^opt/ eV	λ_emi^b/ nm	Stokes/ nm	T_d^c/ ℃	E^ox/V
C4TP	231	5.37	352	122	306	1.50 1.48 —
C6TP	231	5.37	—	—	293
C4TP-MSA	615	2.02	516	—	—

表1. C4TP, C6TP和C4TP-MSA的光物理和电化学数据

Table 1. Optical and electrochemical data for C4TP, C6TP and C4TP-MSA

图4. (a)大环C4TP与酸分子(HAc, HCl, HNO3, TFA, HBr, MSA)作用体系的紫外-可见吸收光谱, 内插图为大环C4TP与酸分子作用体系的溶液在日光下的颜色. (b)大环C4TP与C4TP-MSA作用体系的归一化紫外与荧光光谱, 内插图: 左上和右上分别为C4TP和C4TP-MSA溶液在日光下的颜色, 左下和右下分别为C4TP和C4TP-MSA溶液在365 nm紫外光照射下的颜色

Figure 4. (a) UV-Visible absorption spectra of macrocyclic C4TP interacting with acid molecules (HAc, HCl, HNO3, TFA, HBr, MSA). Insets: The solvent colors of C4TP-acid under daylight; (b) Normalized UV and fluorescence tests of the C4TP-MSA interaction system. Insets: The top left and top right show the colors of C4TP and C4TP-MSA solutions under daylight, respectively; the bottom left and bottom right show the colors of C4TP and C4TP-MSA solutions under 365 nm UV light, respectively

图5. (a)大环C4TP与MSA(物质的量比为1∶1000, 不同时间)作用体系的紫外-可见吸收光谱, 大环C4TP浓度为1.0×10−4 mol•L−1, 溶剂为二氯甲烷, (b) 390 nm和620 nm处峰值强度随时间变化图, (c)大环C4TP与MSA(物质的量比为1∶1000, 不同时间)作用体系溶液的颜色

Figure 5. (a) The UV-Vis absorption spectra of the system where the macrocycle C4TP interacts with MSA (molar ratio as 1∶1000, at different times), with a concentration of C4TP at 1.0×10−4 mol•L−1 and the solvent being dichloromethane; (b) The plot of peak intensities at 390 nm and 620 nm along with time; (c) The color of the solution in the system where the macrocycle C4TP interacts with MSA (molar ratio as 1∶1000, at different times)

图6. (a)大环C4TP与MSA(不同物质的量比, 以大环C4TP为单位1)作用体系的紫外-可见吸收光谱, 大环C4TP浓度为1.0×10−4 mol•L−1, 溶剂为二氯甲烷, (b) 390 nm和620 nm处峰值强度随增加酸物质的量的变化图, (c)大环C4TP与MSA (不同物质的量)作用体系的颜色

Figure 6. (a) The UV-Vis absorption spectra of the system where the macrocycle C4TP interacts with MSA (at different equivalents), with a concentration of C4TP at 1.0×10−4 mol•L−1 with solvent of dichloromethane; (b) The plot of peak intensities at 390 nm and 620 nm along with increasing acid equivalents; (c) The color of the solution in the system where the macrocycle C4TP interacts with MSA (at different equivalents)

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