Research on the Synthesis, Structure and Interactions with Acid of Novel Calixfuran Macrocycle

doi:10.6023/A25010028

Abstract

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

Cite this article

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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Fig. & Tab. 7

Figure 1. Synthetic route of C4TP and C6TP

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

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	—	—

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

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

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)

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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