基于偶氮苯衍生物构筑的Y-MOF的合成、表征及对硝基化合物的荧光检测性能

Synthesis and Characterization of Y-MOF Constructed from Azobenzene Derivatives and Its Fluorescence Detection Performance for Nitro Compounds

摘要

以8-羟基喹啉和5-氨基间苯二甲酸为原料， 通过偶氮反应合成了偶氮苯衍生物（E）-5-[(8-羟基喹啉-5-基)二氮烯基]间苯二甲酸（H₃L）， 并采用溶剂热合成方法将其与稀土离子Y³⁺配位， 制备了金属有机框架（MOF）： {[Y(L)(H₂O)₂]·2.25H₂O}_n； 通过单晶X射线衍射、 热重分析、 红外光谱及粉末X射线衍射分析对其进行了表征. 单晶X射线衍射分析表明， 该MOF的三维网络结构中具有一维孔道； 粉末X射线衍射分析表明， 该MOF在多种有机溶剂及pH=2~12的水溶液中均具有良好的稳定性. 该MOF可以作为荧光传感器， 通过荧光猝灭效应准确检测多种硝基化合物. 实验和理论计算表明， 发光猝灭可归因于MOF与分析物之间的电子转移和共振能量转移两种机制.

Abstract

Using 8-hydroxyquinoline and 5-aminoisophthalic acid as raw materials, an azobenzene derivative, (E)-5-[(8-hydroxyquinolin-5-yl)diazenyl]isophthalic acid(H₃L), was synthesized through an azo reaction. A metal-organic framework(MOF), {[Y(L)(H₂O)₂]·2.25H₂O}_n, was prepared by coordinating H₃L with the rare earth ion Y³⁺ via a solvothermal synthesis method. The MOF was characterized using single-crystal X-ray diffraction analysis, thermogravimetric analysis, infrared spectroscopy, and powder X-ray diffraction analysis. Single-crystal X-ray diffraction analysis revealed that the MOF possesses a three-dimensional network structure with one-dimensional channels. Powder X-ray diffraction analysis demonstrated that the MOF exhibits excellent stability in various organic solvents and aqueous solutions with pH values ranging from 2 to 12. This MOF can serve as an excellent fluorescent sensor for accurately detecting various nitro compounds through fluorescence quenching. Experimental and theoretical calculations indicate that the luminescence quenching can be attributed to electron and resonance energy transfer between the MOF and the analytes. This study contributes to advancing research on MOF materials for their applications as fluorescent sensors.

关键词

金属有机框架 / 晶体结构 / 荧光探针 / 硝基化合物

Key words

Metal-organic framework / Crystal structure / Fluorescence probe / Nitro compound

参考文献

[1] Germain M. E., Knapp M. J., Chem. Soc. Rev., 2009, 38(3), 2543-2555

[2] Salinas Y., Ramon M., Marco M. D., Sancenon F., Costero A. M., Parra M., Gil S., Chem. Soc. Rev., 2012, 41(9), 1261-1296

[3] Lease N., Kay L., Chavez D. E., Robbins D., Manner V. W., J. Hazard. Mater., 2019, 367, 546-549

[4] Sun X., Wang Y., Lei Y., Chem. Soc. Rev., 2015, 44(22), 8019-8061

[5] Nagarkar S. S., Joarder B., Chaudhari A. K., Mukherjee S., Ghosh S. K., Angew. Chem. Int. Ed., 2013, 52(10), 2881-2885

[6] Kreno L. E., Leong K., Farha O. K., Allendorf M., Duyne R. P. V., Hupp J. T., Chem. Rev., 2012, 112(2), 1105-1125

[7] Lemaire A., Hapiot P., Geneste F., Anal. Chem., 2019, 91(4), 2797-2804

[8] Zhan Z., Liang X., Zhang X., Jia Y., Hu M., Dalton Trans., 2019, 48(5), 1786-1794

[9] Senthilkumar S., Goswami R., Smith V. J., Bajaj H. C., Neogi S., ACS Sustain. Chem. Eng., 2018, 6(8), 10295-10306

[10] Gong W., Zhou L., Chem. J. Chinese Universities, 2025, 46(7), 20250062

[11] (龚文鹏, 周林楠. 高等学校化学学报, 2025, 46(7), 20250062)

[12] Thomas S. W., Joly G. D., Swager T. M., Chem. Rev., 2007, 107(4), 1339-1386

[13] Huang X., Chen C., Xu C., Ma J., Yang L., Wang W., Dou W., Liu W., Chem. Eur. J., 2019, 25(4), 1090-1097

[14] Mukherjee P. S., Acharyya K., Angew. Chem. Int. Ed., 2019, 58(17), 5623-5628

[15] Lan A., Li K., Wu H., Olson D. H., Emge T. J., Ki W., Hong M., Li J., Angew. Chem. Int. Ed., 2009, 48(13), 2334-2338

[16] Zhang C., Yan Y., Sun L., Liang Z., Li J., CrystEngComm, 2016, 18(22), 4102-4108

[17] Zhang X., Luo X., Zhang N., Wu J., Huang Y. Q., Inorg. Chem. Front., 2017, 4(11), 1888-1894

[18] Luo X., Zhang X., Duan Y., Wang X., Zhao J., Dalton Trans., 2017, 46(19), 6303-6311

[19] Sheldrick G. M., Acta Cryst., 2015, C71, 3-8

[20] Zhao S., Yao J., Fan Q., Yuan Y., Tu S., Wu Y., Xia Q., Sep. Purif. Technol., 2024, 330, 125256

[21] Echenique-Errandonea E., Pérez J. M., Rojas S., Cepeda J., Seco J. M., Fernández I., Rodríguez-Diéguez A., Dalton Trans., 2021, 50(34), 11720-11724

[22] Welty C., Gormley E. L., Oppenheim J. J., Dinca M., Hendon C. H., Stadie N. P., ACS Mater. Lett., 2024, 6(8), 3909-3914

[23] Wu M., Zhang H., Ge C., Wu J., Ma S., Yuan Y., Zhao L., Yao T., Zhang X., Yang Q., Spectrochim. Acta A, 2022, 264, 120276

[24] Zhuang X., Zhang X., Zhang N., Wang Y., Zhao L., Qang Q., Cryst. Growth Des., 2019, 19(10), 5729-5736

[25] Cao L. H., Shi F., Zhang W. M., Zang S. Q., Mak T. C..W., Chem. Eur. J., 2015, 21(44), 15705-15712

[26] Wang X. S., Li L., Yuan D. Q., Huang Y. B., Cao R., J. Hazard. Mater., 2018, 344, 283-290

[27] Meng Y., Zhang N., Li J., Xu Y., Yang Q., Yuan Y., Zhang X., Wu J., Zhao L., Spectrochim. Acta A, 2022, 266, 120419

[28] Guo X. Z., Zhang J., Lin B., Xiong G. Z., Zhang X. X., Li Z. C., Gui L., Si Y., Chen S. S., Qiu Z., J. Mol. Struct., 2024, 1304, 137569

[29] Yang L., Tian M., Qin J., Lu Y., Yu Q., Han J. M., Eur. J. Inorg. Chem., 2023, 26, e202300089

[30] Xin X., Jing Y., Li P., Zhang X., Li J., Li L., Zhang L., Cryst. Growth Des., 2023, 23(6), 3988-3995

[31] Huang J. J., Zhao D., Yin G. J., Chinese J. Struct. Chem., 2022, 41, 2203030

[32] (黄晶晶, 赵丹, 尹国杰. 中国结构化学杂志, 2022, 41, 2203030)

[33] Pathak C., Seth S., Polyhedron, 2026, 283, 117857

[34] Zhuang X., Zhang N., Zhang X., Wang Y., Zhao L., Yang Q., Microchem. J., 2020, 153, 104498

[35] Joarder B., Desai A. V., Samanta P., Mukherjee S., Ghosh S. K., Chem. Eur. J., 2015, 21(3), 965-969

基金资助

国家自然科学基金(22575069)