From Tetrahedral Tetraphosphonic Acids E[ p ‐C 6 H 4 P(O)(OH) 2 ] 4 (E=C, Si) to Porous Cu‐ and Zn‐MOFs with Large Surface Areas

This study describes the porous MOFs Cu 2 H 4 STPPA⋅2 H 2 O ( 1 ⋅2 H 2 O), Zn 2 H 4 STPPA ( 2 ) and Zn 2 H 4 MTPPA ( 3 ) obtained using the tetrahedral linkers tetraphenylmethane tetrakis‐4‐phosphonic acid (H 8 MTTPA) and tetraphenylsilane tetrakis‐4‐phosphonic acid (H 8 STPPA) under solvothermal conditions. X‐ray structures reveal 3D frameworks with large assessable voids. The percentage void volumes and the specific BET surface areas of 1 (48.7 %, 794 m 2 /g), 2 (48.1 %, 565 m 2 /g) and 3 (51.3 %, 927 m 2 /g) predicted by molecular simulations are among the highest reported for MOFs derived from phosphonic acids.