New Group 13 MIL‐53 Derivates based on 2,5‐Thiophenedicarboxylic Acid

A new rigid metal‐organic framework (MOF) with MIL‐53 topology built of 2,5‐thiophenedicarboxylate (TDC) and Al, Ga, or In is reported. Its structure contains chains of trans corner sharing MO 6 octahedra, connected by the linker molecules to form microporous square shaped 1D channels. A combination of powder X‐ray diffraction (PXRD), density functional theory (DFT) calculations, and 1 H, 13 C, and 27 Al solid‐state NMR spectroscopy (ssNMR) was used to analyse the structures in detail. The synthesis is easily scaled‐up using microwave assisted solvothermal conditions. All materials possess a high thermal stability up to 420 °C in air and permanent porosity towards N 2 , H 2 , CO 2 , and CH 4 . Al‐MIL‐53‐TDC shows a high specific surface area of a s,BET = 1150 m 2 · g –1 with a micropore volume of V mic = 0.48 cm 3 · g –1 as well as water uptake of 5.5H 2 O molecules per sum formula (469 mg · g –1 ) with an a sigmoidal shape, advantageous for heat‐transformation processes. Noteworthy, this material adsorbs 2.1 wt % H 2 at –196 °C and 1 bar, which surpasses other Al‐MIL‐53 compounds based on linear functionalized terephthalates.