The bicyclic ditopic linker 2,2′-biselenophene-5,5′-dicarboxylic acid (H2SpSp), 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 fivemembered 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.
Zirconium metal−organic frameworks containing a biselenophene linker: Synthesis, characterization, and luminescent properties / Mercuri G.; Moroni M.; Fermi A.; Bergamini G.; Galli S.; Giambastiani G.; Rossin A.. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - STAMPA. - 59:21(2020), pp. 15832-15841. [10.1021/acs.inorgchem.0c02297]
Zirconium metal−organic frameworks containing a biselenophene linker: Synthesis, characterization, and luminescent properties
Fermi A.
;Bergamini G.;
2020
Abstract
The bicyclic ditopic linker 2,2′-biselenophene-5,5′-dicarboxylic acid (H2SpSp), 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 fivemembered 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.File | Dimensione | Formato | |
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