Design and synthesis of pillared metal–organic frameworks featuring olefinic fragments

Abstract

While metal–organic frameworks (MOFs) are known primarily for their well-defined crystalline porous structures that make them desirable for a myriad of applications, they also distinguish themselves with their chemical tunability. One strategy for chemical tailoring of MOF structures is post-synthetic modification (PSM) targeting moieties present in their organic building blocks (linkers). In this context, alkene (olefinic) fragments are underrepresented in the realm of MOFs despite their extremely well-established and versatile chemistry. With the majority of reported olefinic MOFs falling into the microporous regime, the PSM opportunities involving bulkier reagents are severely limited. Herein, we report a family of UofT (University of Toronto) pillared MOFs constructed around olefinic 1,4-bis(2-(pyridin-4-yl)vinyl)benzene (BPVB) and tetrakis(4-carboxyphenyl)porphyrin (TCPP) linkers. By utilizing a variety of M(II) [M = Zn, Ni, Co] precursors, three structurally distinct frameworks were synthesized and characterized. Most notably, the nickel-based framework represents the first reported example of a stable mesoporous olefinic pillared MOF. In addition to the de novo formation of a stable pillared MOF, Ni(II) is also used in a cation exchange process to structurally reinforce zinc-based frameworks.

Graphical abstract: Design and synthesis of pillared metal–organic frameworks featuring olefinic fragments

Supplementary files

Article information

Article type
Paper
Submitted
23 Aug 2024
Accepted
03 Oct 2024
First published
05 Oct 2024

Dalton Trans., 2024, Advance Article

Design and synthesis of pillared metal–organic frameworks featuring olefinic fragments

R. L. Mander, A. Schmidt, M. Ruf and M. D. Korzyński, Dalton Trans., 2024, Advance Article , DOI: 10.1039/D4DT02397H

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