[Al2(OH)2(TCPB)] An Al-MOF based on a tetratopic linker molecule

High-throughput methods were employed in the discovery and synthesis optimization of the new microcrystalline metal-organic framework (MOF) [Al-2(OH)(2)(TCPB)] 2 DMF (denoted CAU-9as), which contains the tetratopic linker ion 1,2,4,5-tetrakis-(4-carboxylatophenyl)-benzene (TCPB4-). The compound is obtained under solvothermal reaction conditions and activation at 150 degrees C leads to the removal of the guest molecules (CAU-9act). Detailed characterization was carried out by FT-IR and NMR spectroscopy, thermogravimetric analysis, gas sorption measurements and X-ray powder diffraction. CAU-9act crystallizes in an orthorhombic unit cell (space group Cmmm) with the cell parameters: a = 31.562(4), b = 6.642(7), c = 10.6612(7) angstrom. Modeling by force field calculations in combination with Rietveld refinement was used to determine the structure of CAU-9. The content of the asymmetric unit was corroborated based on NMR crystallographic strategies evaluating high-resolution H-1, C-13 and (27)AI MAS NMR spectra. The structure of CAU-9 is isoreticular to the one of MIL-118B [Al-2(OH)(2)(BTEC)] (BTEC = 1,2,4,5-benzenetetracarboxylate) and Al-PMOF [Al-2(OH)(2)(TCPP)] (TCPP = meso-tetra(4-carboxylato-phenyl)porphyrin). According to the temperature dependent PXRD measurements and the thermogravimetric analysis, it is stable up to 480 degrees C in air. The nitrogen sorption measurement at 77 K has given a Brunauer Emmett Teller (BET) surface area of 1118 m(2) g(-1) and a micropore volume of 0.45 cm(3) g(-1). In contrast to MIL-118 no rearrangement of the carboxylate groups from a mono-to bidentate coordination mode was observed upon activation. (C) 2015 Elsevier Inc, All rights reserved.