Zirconium Metal–Organic Frameworks Containing a Biselenophene Linker: Synthesis, Characterization, and Luminescent Properties

• Published in: Inorganic chemistry 2020-11, Vol.59 (21), p.15832-15841
• Main Authors: Mercuri, Giorgio, Moroni, Marco, Fermi, Andrea, Bergamini, Giacomo, Galli, Simona, Giambastiani, Giuliano, Rossin, Andrea
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.0c02297

The bicyclic ditopic linker 2,2′-biselenophene-5,5′-dicarboxylic acid (H 2 SpSp), specifically designed for metal–organic framework (MOF) construction, has been synthesized in good yield and fully characterized. The corresponding zirconium MOF (Zr-MOF) [Zr6O4(OH)4(SpSp)3.8Cl4.4] (1; where missing linkers are replaced by chloride anions as shown by X-ray fluorescence and elemental analysis) is isostructural with its bithiophene and bithiazole analogues. Starting from 1, an extension of the biselenophene-based Zr-MOF family has been successfully achieved, exploiting the structural analogy of the five-membered heterocycles selenophene, thiophene, and thiazole. Thus, three mixed-linker MOFs containing variable amounts of different bis­(heterocyclic) dicarboxylic acids have been prepared and fully characterized: the two double-mixed [Zr6O4(OH)4(SpSp)2.6(TpTp)1.3Cl4.2] (2; H2TpTp = 2,2′-bithiophene-5,5′-dicarboxylic acid) and [Zr6O4(OH)4(SpSp)2(TzTz)1.8Cl4.4] (3; H2TzTz = 2,2′-bithiazole-5,5′-dicarboxylic acid) materials, as well as the triple-mixed [Zr6O4(OH)4(SpSp)1.6(TpTp)1.2(TzTz)1.4Cl3.6] (4) compound. The four MOFs are luminescent under UV irradiation, exhibiting emission wavelengths falling in the blue-green visible region, as observed for their constitutive linkers. These materials open new horizons in the preparation of porous luminescent sensors or multicolor emitters for light-emitting diodes.