Alkali Phosphonate Metal–Organic Frameworks

Abstract

An ew family of porousm etal-organic frameworks (MOFs), namely alkali phosphonate MOFs,i sr eported. [Na 2 Cu(H 4 TPPA)]·(NH 2 (CH 3 ) 2 ) 2 (GTUB-1)w as synthesized using the tetratopic 5,10,15,20-tetrakis[p-phenylphosphonic acid] porphyrin (H 8 -TPPA)l inker with planar X-shaped geometrical core. GTUB-1 is composed of rectangular void channels with BET surface area of 697 m 2 g À1 . GTUB-1 exhibits exceptional thermal stability.T he toxicitya nalysis of the (H 8 -TPPA)l inker indicatest hat it is well tolerated by an intestinal cell line, suggesting its suitability for creating phosphonate MOFs for biological applications.[a] M.Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

Probing Isoreticular Expansions in Phosphonate MOFs and their Applications

“…Schematic visualization of planar porphyrin core and saddle conformation. Double bonds omitted for clarity …”

“…Amongst all known MOFs, the phosphonate‐based frameworks play only a niche role so far . Despite the limited number of phosphonate MOFs reported in the literature they have already created diverse applications in proton conductivity, catalysis, magnetism etc., and they exhibit potential in forming future non‐toxic MOFs, which are suitable for biological and food chemistry applications . The recent interest in phosphonate MOFs have been summarized in several review articles , .…”

“…Such linker geometries prohibited the formation of hydrophobic layers and created the large pore sites. The second approach relied on planar tritopic and tetratopic linkers where the phosphonate arms are separated by 90° and 120° angles , , . Although, such planar linkers follow the same mechanism of crystallization observed in pillared layered and lamellar phosphonates.…”

Semiconductive Microporous Hydrogen-Bonded Organophosphonic Acid Frameworks

“…The H8-TPPA linker was synthesized according to our previously reported method involving a Pdcatalyzed Arbuzov reaction [50] , in order to avoid the porphyrin core being occupied by Ni(II) after a Nicatalyzed Arbuzov reaction [49,51] . The synthesized metal-free H8TPPA linker eliminated the possibility of metal-ligand interactions that could have triggered the formation of MOFs.…”

A Semiconductive and Microporous One-Dimensional Tubular Metal-Organic Framework

“…Due to the large ionic radius of the Pd atom, it does not readily incorporate into the porphyrin ring, allowing one to incorporate other metal atoms into the porphyrin core. [34,40] Later, we introduced square planar Cu(II) into H8-TPPA's imidazole ring to synthesize Cu-H8TPPA (the deprotonated imidazole hydrogens are omitted in this formula). GTUB-4 was synthesized in a DMF/H2O and phenylphosphonic acid (modulator) mixture at 80 °C for 24 h, giving rise to long purple needle crystals in high yield (see SI for experimental details).…”