期刊
INORGANIC CHEMISTRY
卷 60, 期 12, 页码 8861-8869出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.1c00767
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资金
- Deutsche Forschungsgemeinschaft [STO 643/10-1]
- Swedish Foundation for Strategic Research (SSF)
This study systematically investigated Ga-containing metal-organic frameworks using six V-shaped linker molecules with different sizes, geometries, and additional functional groups. Four new Ga-MOFs isoreticular with their aluminum counterparts and two non-isostructural Ga-MOFs were obtained. The detailed structural characterization and sorption properties of the compounds were analyzed, showing remarkable findings in crystal structures and water sorption capabilities.
Following the concept of isoreticular chemistry, we carried out a systematic study on Ga-containing metal-organic frameworks (MOFs) using six V-shaped linker molecules of differing sizes, geometries, and additional functional groups. The linkers included three isophthalic acid derivatives (m-H2BDC-R, R = CH3, OCH3, NHCOCH3), thiophene-2,5-dicarboxylic acid (H2TDC), and two 4,4'-sulfonyldibenzoic acid derivatives (H(2)SDBA, DPSTA). The crystal structures of seven compounds were elucidated by a combination of model building, single-crystal X-ray diffraction (SCXRD), three-dimensional electron diffraction (3D ED), and Rietveld refinements against powder X-ray diffraction (PXRD) data. Four new Ga-MOFs that are isoreticular with their aluminum counterparts, i.e. Ga-CAU-10-R (Ga(OH)(m-BDC-R); R = OCH3, NHCOCH3), Ga-CAU-11 (Ga(OH)(SDBA)), and Ga-CAU-11-COOH (Ga(OH)(H2DPSTC)), were obtained. For the first time large single crystals of a MOF crystallizing in the CAU-10 structure type could be isolated, i.e. Ga-CAU-10-OCH3, which permitted a detailed structural characterization. In addition, the use of 5-methylisophthalic acid and thiophene-2,5-dicarboxylic acid resulted in two new Ga-MOFs denoted Ga-CAU-49 and Ga-CAU-51, respectively, which are not isostructural with any known Al-MOF. The crystal structure of Ga-CAU-49 ([Ga-4(m-HBDC-CH3)(2)(m-BDC-CH3)(3)(OH)(4)(H2O)]) contains an unprecedented rod-shaped inorganic building unit (IBU) of the formula(infinity)(1) {Ga-16(OH)(18)O-60}, composed of corner-sharing GaO5 and GaO6 polyhedra. In Ga-CAU-51 ([Ga(OH)(C5H2O2S)]) chains of alternating cis and trans corner-sharing GaO6 polyhedra form the IBU. A detailed characterization of the title compounds was carried out, including nitrogen gas and water vapor sorption measurements. Ga-CAU-11 was the only compound exhibiting porosity toward nitrogen with a type I isotherm, a specific surface area of a(S,BET) = 210 m(2)/g, and a micropore volume of V-mic = 0.09 cm3/g. The new MOF Ga-CAU-51 exhibits exceptional water sorption properties with a reversible S-shaped isotherm and a high uptake around p/p(0) = 0.38 of m(ads) = 370 mg/g.
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