Phosphonate Monoesters as Carboxylate-like Linkers for Metal Organic Frameworks

Abstract

Bidentate phosphonate monoesters are analogues of popular dicarboxylate linkers in MOFs, but with an alkoxy tether close to the coordinating site. Herein, we report 3-D MOF materials based upon phosphonate monoester linkers. Cu(1,4-benzenediphosphonate bis(monoalkyl ester), CuBDPR, with an ethyl tether is nonporous; however, the methyl tether generates an isomorphous framework that is porous and captures CO(2) with a high isosteric heat of adsorption of 45 kJ mol(-1). Computational modeling reveals that the CO(2) uptake is extremely sensitive both to the flexing of the structure and to the orientation of the alkyl tether.

Structural and spectroscopic characterization of two new layered uranyl(VI) p-xylenediphosphonate compounds synthesized via ionothermal method

“…During the last several decades, the field of metal phosphonates has received increasing attention owing to their potential applications in catalysis [1,2], proton conductivity [3][4][5], gas absorption and separation [6][7][8], magnetism [8][9][10][11], and optics [12]. The crystal chemistry of actinide phosphonates is an important subfield of metal phosphonates, where major attention was paid to uranium [13][14][15][16][17][18][19] and thorium [20][21][22], with only a few neptunium [22][23][24], plutonium [25][26][27][28], and americium [28] complexes.…”

Hydrophobic Metal–Organic Frameworks: Assessment, Construction, and Diverse Applications

“…Shimizu's group reported a series of MOFs derived from phosphonate monoesters, some of which have been proven as hydrophobic . In 2012, they reported a barium tetraethyl‐1,3,6,8‐pyrenetetraphosphonate MOF, CALF‐25, from the solvothermal reaction of BaBr 2 and the ligand optp, which turned into a phosphonate monoester by in situ partial hydrolysis .…”

P–C Bond Cleavage-Assisted Lanthanide Phosphate Coordination Polymers

“…[23][24][25][26][27][28] To some extent this work has also been extended to phosphonate/phosphate ligands. [32][33][34] We have a long-standing interest in the use of phosphonate ligands for the preparation of polynuclear molecular assemblies whose nuclearity can be tuned over a wide range by the use of synthetic methods that include variation of the steric bulk on the phosphonate ligand and/or the use of an ancillary nitrogen ligand. [35][36][37][38][39][40][41][42][43][44] More recently we have started to engage in the chemistry of polynuclear lanthanide complexes from a molecular magnetism standpoint.…”