Highly stable and porous porphyrin-based zirconium and hafnium phosphonates – electron crystallography as an important tool for structure elucidation

The Ni-metallated porphyrin-based tetraphosphonic acid (Ni-tetra(4-phosphonophenyl)porphyrin, Ni-H(8)TPPP) was used for the synthesis of highly porous metal phosphonates containing the tetravalent cations Zr(4+) and Hf(4+). The compounds were thoroughly characterized regarding their sorption properties towards N(2) and H(2)O as well as thermal and chemical stability. During the synthesis optimization the reaction time could be substantially decreased under stirring from 24 to 3 h in glass vials. M-CAU-30, [M(2)(Ni-H(2)TPPP)(OH/F)(2)]·H(2)O (M = Zr, Hf) shows exceptionally high specific surface areas for metal phosphonates of a(BET) = 1070 and 1030 m(2) g(–1) for Zr- and Hf-CAU-30, respectively, which are very close/correspond to the theoretical values of 1180 and 1030 m(2) g(–1). CAU-30 is always obtained as mixtures with one mol ZrO(2)/HfO(2) per formula unit as proven by TEM, electron diffraction, TG and elemental analysis. Hence experimentally derived specific surface areas are 970 and 910 m(2) g(–1), respectively. M-CAU-30 is chemically stable in the pH range 0 to 12 in HCl/NaOH and thermally up to 420 °C in air as determined by variable-temperature powder X-ray diffraction (VT-PXRD). The crystal structure of M-CAU-30 was determined by combining electron diffraction tomography for structure solution and powder X-ray diffraction data for the structure refinement. The crystal structure consists of chains of corner sharing MO(6) octahedra interconnected by the partly deprotonated linker molecules Ni-H(2)TPPP(6–). Thus 1D channels with pore diameters of 1.3 × 2.0 nm are formed. The redox activity of Zr-CAU-30 was investigated by cyclic voltammetry resulting in a reversible redox process at a half-wave potential of E(1/2) = –0.649 V.