Crystalline and permanently porous porphyrin-based metal tetraphosphonates

Abstract

The new porphyrin-based tetraphosphonic acid (Ni-HTPPP) was employed in the synthesis of four isostructural MOFs of composition [M(Ni-HTPPP)(HO)], denoted CAU-29 (M = Mn, Co, Ni, Cd). Ni-CAU-29 was thoroughly characterized regarding its thermal and chemical stability as well as for proton conductivity.

Highly Proton‐Conductive Zinc Metal‐Organic Framework Based On Nickel(II) Porphyrinylphosphonate

“…Only three of the four phosphonate groups take part in the framework formation, and each Ni‐H 3 TPPP molecule acts as a tritopic linker, which is unusual for porphyrin MOFs (Figure c). The P−O distances of the coordinated phosphonate groups are within 1.493(4)–1.552(4) Å, which are similar to those observed for Ni‐CAU‐29 . The fourth phosphonate does not bind to zinc ions, but assists in the generation of stable 3D porous framework through hydrogen bonding with adjacent porphyrin molecules.…”

“…Porphyrins, which have rigid structures, additional coordination sites and tunable periphery, are suitable organic building blocks for the construction of MOFs. Surprisingly, the examples of phosphonate‐substituted porphyrin‐based MOFs are limited . All of them, except for the material described in, include the nickel(II) porphyrinylphosphonate (Ni‐H 8 TPPP) as an organic moiety, and only one MOF possesses a moderate proton conductivity .…”

“…Surprisingly,t he examples of phosphonate-substituted porphyrin-based MOFs are limited. [34][35][36][37] All of them,e xcept for the materiald escribed in, [35] include the nickel(II) porphyrinylphosphonate (Ni-H 8 TPPP) as an organic moiety,a nd only one MOF possesses am oderate protonc onductivity. [36] In general, there are few examples of proton-conductive MOFs based on porphyrins.…”

“…[34][35][36][37] All of them,e xcept for the materiald escribed in, [35] include the nickel(II) porphyrinylphosphonate (Ni-H 8 TPPP) as an organic moiety,a nd only one MOF possesses am oderate protonc onductivity. [36] In general, there are few examples of proton-conductive MOFs based on porphyrins. [38][39][40] Therefore, the developmento fa ne fficient strategy towards MOFs based on porphyrinylphosphonates with proton conductivity is ap articularly important scientific challenge.Here, we present an ew originals ynthetic approach towards high proton-conductive nickel(II) porphyrinylphosphonate basedM OF [Zn 3 (Ni…”

A Porous Cobalt Tetraphosphonate Metal–Organic Framework: Accurate Structure and Guest Molecule Location Determined by Continuous‐Rotation Electron Diffraction

“…MOFs have shown wide applications such as gas storage and separation, drug delivery and catalysis . Although most porphyrin‐based MOFs have been obtained using tetracarboxyporphyrin (H 6 TCPP) as the linker, only two with the Ni‐(4‐tetraphosphonophenylporphyrin) (Ni‐H 8 TPPP) linker have been reported . This observation is in line with the fewer number of known porous metal phosphonates in comparison to porous metal carboxylates .…”