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New Al-MOFs Based on Sulfonyldibenzoate Ions: A Rare Example of Intralayer Porosity.
- Source :
-
Inorganic Chemistry . 1/19/2015, Vol. 54 Issue 2, p492-501. 10p. - Publication Year :
- 2015
-
Abstract
- A new sulfone-functionalized metal-organic framework [Al(OH)(SDBA)]·0.25DMF, denoted CAU-11, was synthesized using a V-shaped linker molecule 4,4'-sulfonyldibenzoic acid (H2SDBA). The crystal structure was solved from synchrotron X-ray powder diffraction data. Chains of trans corner-sharing AlO6 octahedra are interconnected by the carboxylate groups to form layers (ABAB stacking). Within the layers, hydrophobic lozenge-shaped pores with a diameter of 6.4 × 7.1 Ų are present inducing permanent porosity (aBET = 350 m² g-1 and Vmicro = 0.17 cm³ g-1). With the application of HT-methods (HT = high throughput), the isoreticular carboxylate functionalized compound [Al(OH)(H2DPSTC)]·0.5H2O (CAU-11-COOH) was synthesized using the linker molecule 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DPSDA), which hydrolyzes under the reaction conditions. Due to the additional noncoordinating carboxylic acid groups the pores are hydrophilic. Changing the molar ratio of Al3+ to linker lead to the discovery of a second new compound [Al2(OH)2(DPSTC)(H2O)2]·0.5H2O (CAU-12). In CAU-12 the linker molecule is fully deprotonated which leads to different connectivity compared to the structure of CAU-11-COOH. Thermal activation of CAU-12 leads to dehydration and transformation of the structure to [Al2(OH)2(DPSTC)]·nH2O (CAU-12-dehy). Coordinated water molecules were removed, and the coordination site is replaced by the previously noncoordinating O atom of the adjacent carboxylate group. The SO2-groups point into the pores resulting in a highly hydrophobic three-dimensional framework. The compounds exhibit high thermal stability in air at least up to 420 °C. Synthesis of CAU-11 can be easily scaled up in very high yields (98%). [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00201669
- Volume :
- 54
- Issue :
- 2
- Database :
- Academic Search Index
- Journal :
- Inorganic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 101204354
- Full Text :
- https://doi.org/10.1021/ic502242j