Mediating Order and Modulating Porosity by Controlled Hydrolysis in a Phosphonate Monoester Metal–Organic Framework

Abstract

A crystalline and permanently porous copper phosphonate monoester framework has been synthesized from a tetraaryl trigonal phosphonate monoester linker. This material has a surface area over 1000 m g , as measured by N sorption, the highest reported for a phosphonate-based metal-organic framework (MOF). The monoesters result in hydrophobic pore surfaces that give a low heat of adsorption for CO and low calculated selectivity for CO over N and CH in binary mixtures. By careful manipulation of synthetic conditions, it is possible to selectively remove some of the monoesters lining the pore to form a hydrogen phosphonate while giving an isomorphous structure. This increases the affinity of the framework for CO giving higher ambient uptake, higher heat of adsorption, and much higher calculated selectivity for CO over both N and CH . Formation of the acid groups is noteworthy as complexation with the parent acid gives a different structure.

Spectrally-resolved third-harmonic generation and the fundamental role of O–H⋯Cl hydrogen bonding in Oh, Td-cobalt(ii) tetraphenylmethane-based coordination polymers

“…Noteworthily, this CP is a centrosymmetric analogue related to SHG-active phosphonate-ester non-centrosymmetric CPs. 11 As a result of its peculiar structure, apart from NLO studies, CP 2-Cl gave us the possibility to investigate unusual for most of the phosphonates [14][15][16][17][18][19][20][21][22][23] and phosphonate monoester [24][25][26][27][28] CPs structural aspects, important from the viewpoint of crystal engineering. It is the moderate strength of dialkylphosphonate binding via phosphoryl (PvO) donor coordination combined with the bulkiness of this functional group that induces monodentate axial binding of metal ions.…”

Preise von CSC und CIC 2019

“…Von besonderem Interesse sind dabei robuste MOFs und die Übertragung der Forschung auf höhere Technologieebenen mithilfe von Kooperationen. Die Gruppe berichtete über die kontrollierte Hydrolyse eines Phosphonatmonoester‐MOF, um Ordnung und Porosität zu modulieren, in der Angewandten Chemie und über die Anordnung von Mikrokügelchen durch Phosphonatmonoester‐Koordination in Chemistry—A European Journal …”

Layered Simple Hydroxides Functionalized by Fluorene‐Phosphonic Acids: Synthesis, Interface Theoretical Insights, and Magnetoelectric Effect

“…[25] Most of the preceding layered functional materials are characterized by weak bonds between subnetworks, which may limit synergy between properties. [32,33] Phosphonic acids, due to their coordination properties, are widely employed to prepare crystalline hybrid materials [34] that are studied for their porosity, [35,36] ionic conduction, [37,38] magnetic, [39,40] or fluorescent [41,42] properties or for their bactericidal effects. The X n− anion located in the interlayer space may be substituted by a large variety of molecules via anionic exchange reaction.…”