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

Abstract

A highly porous and stable Zr-MOF containing a planar porphyrin-based tetraphosphonic acid was synthesized and characterized regarding its sorption properties and chemical stability.

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

“…[1,3,[5][6][7] Although most porphyrin-based MOFs have been obtained using tetracarboxyporphyrin (H 6 TCPP) as the linker,o nly two with the Ni-(4-tetraphosphonophenylporphyrin) (Ni-H 8 TPPP) linker have been reported. [8,9] This observation is in line with the fewer number of knownp orous metal phosphonates in comparison to porous metal carboxylates. [10,11] In terms of cobalt MOFs, only four porousc obalt phosphonate-based MOFs are currently known.…”

“…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 .…”

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

“…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.…”

Expanding the Variety of Zirconium‐based Inorganic Building Units for Metal–Organic Frameworks

“…[10] This IBU is composed of hexagonally arranged m-OH bridged {Zr 6 O 8 }c lusters which are interconnected by 2,5-pyrazinedicarboxylate ions.A different and less frequently observed IBU is represented by the 1D chain of ZrO 7 polyhedra within the MIL-140 series. In the last decade,e lectron crystallography has shown its power and successful applications in structure analysis of nanocrystalline materials with challenging structural features [26][27][28][29][30][31][32] like extra-large lattice parameters, disorder,p seudo-symmetry,s mall crystalline domains,m ultiple phases and detection of light scattering atoms (e.g., Li, B, H). In the last decade,e lectron crystallography has shown its power and successful applications in structure analysis of nanocrystalline materials with challenging structural features [26][27][28][29][30][31][32] like extra-large lattice parameters, disorder,p seudo-symmetry,s mall crystalline domains,m ultiple phases and detection of light scattering atoms (e.g., Li, B, H).…”