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Functionalization of phosphinate MOFs on organic linkers as a method of tuning their proton conductivity and other properties

Authors: Hynek Jan | Ondrušová Soňa | Ramteke Prajakta Mohan | Kloda Matouš | Bůžek Daniel | Demel Jan | Plecháček Tomáš | Beneš Ludvík | Melánová Klára

Year: 2025

Type of publication: ostatní - přednáška nebo poster

Page from-to: nestránkováno

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Language	Name	Abstract	Keywords
eng	Functionalization of phosphinate MOFs on organic linkers as a method of tuning their proton conductivity and other properties	The family of ICR MOFs is based on phosphinate linker molecules and trivalent metallic nodes (Fe3+, Al3+). In past, we reported numerous isoreticular structures showing exceptional chemical stability and specific surface area up to 1300 m2·g–1. [1] These materials accommodate a reasonable amount of bisphenol A, a rather hydrophobic pollutant of emerging concern; however, their applicability for the adsorptive removal of more polar pollutants and proton conductivity is limited by the hydrophobic character of the pore walls. [2] We present the recent advances in preparation of phosphinate and phosphonate MOFs with hydrophilic pore walls suitable for adsorptive removal of polar pollutants and proton conductivity. One possible direction is employment of linker molecules containing additional polar functional groups (carboxylates, amines). Isoreticular derivatives of ICR-7 substituted with –NMe2 and –COOEt groups (ICR-8 and ICR-14, respectively), which were prepared from the correspondingly derivatized linkers, reveal a higher affinity toward polar pollutants (diclofenac, cephalexin, sulfamethoxazole) [3]. The carboxylated derivatives of phosphinate linkers (e.g. H2BBP(CH2COOH) shown below) can also provide structures of ICR-28 and ICR-29 with tetragonal and hexagonal morphology, respectively, where the carboxylate groups are protonated. ICR-29 reveal a significantly higher water vapour adsorption than isoreticular ICR-6, which we believe will bring an improvement in adsorption of polar pollutants and proton conductivity. Another possible strategy to improve the functional properties of the MOFs is employment of the linkers based on pyridine or 4,4’-bipyridine. These ligands contain multiple functional groups, which can partially stay uncoordinated and serve as a donors or acceptors of protons and therefore facilitate the proton conductivity. [1] J. Hynek, P. Brázda, J. Rohlíček, M. G. S. Londesborough, J. Demel, Angew. Chem. Int. Ed. 57 (2018) 50	MOF; preparation; chemical stability specific surface area°°