Synthesis and Fluorescent Properties of Metal-Organic Frameworks Based on 4,4'-Azobenzoic Acid

Abstract

Abstract: Using pyrazine and 4,4'-bipyrine as co-ligand, respectively, two metal-organic frameworks (MOFs) were synthesized by complexzation of Cd²⁺ and Zn²⁺ with 4,4'-azobenzoic acid (H₂(4,4'-azo)). X-ray single crystal diffraction shows that their crystal structures are as same as those of the previously published [Cd(4,4'-azo)(H₂O)]_n (1) and [Zn(4,4'-azo)(H₂O)₂]_n (2) where the co-ligands are not involved into the structures. Varying the co-ligand to 1,3-bi(tetrapyridyl)propane (bpp) with larger size and metal ions to Co²⁺, a co-crystal [H₂(4,4'-azo)(bpp)]_n (3) was isolated successfully, which is monoclinic, space group of C2/c with crystal cell parameters a=3.216 8(19) nm, b=0.475 5(3) nm and c=1.873 2(14) nm. The thermal stabilities of the three compounds were investigated by thermal gravimetric analyzer and the fluorescence of two MOFs were examined by fluorescence spectrometer, respectively. Both 1 and 2 display excellent thermal stabilities. Especially, 2 keeps stable up to 247 ℃. UV-Vis spectra and fluorescence spectra of 1 and 2 are different, which are ascribed to that 1 is a 3D network formed by 4,4'-azo bi-dentated coordinating with two Cd²⁺ whereas 2 is a 1D zig-zag chain constructed by 4,4'-azo mono-dentated coordinating with Zn²⁺. In addition to the ligand emission at 359 nm, 2 exhibits a new enhanced emission at 420 nm due to the ligand to metal charge transfer (LMCT) upon Zn²⁺ coordination with 4,4'-azo.

Key words: 4,4'-azobenzoic acid, metal-organic framework, crystal structure, fluorescence, charge transfer, thermal stability

CLC Number:

O641
O627

YU Zhong, WANG Yuxue, DAI Ping, HAN Jing, WANG Yan, ZHANG Xu. Synthesis and Fluorescent Properties of Metal-Organic Frameworks Based on 4,4'-Azobenzoic Acid[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2023, 52(11): 2024-2033.

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