Issue 64, 2022

Acetylenedicarboxylate as a linker in the engineering of coordination polymers and metal–organic frameworks: challenges and potential

Abstract

Despite its simplicity as a short and rod-like linear linker, acetylenedicarboxylate (ADC) has for a long time been somewhat overlooked in the engineering of coordination polymers (CPs) and especially in the construction of porous metal–organic frameworks (MOFs). This situation seems to be stemming from the thermosensitivity of the free acid (H2ADC) precursor and its dicarboxylate, which makes the synthesis of their CP- and MOF-derivatives, as well as the evacuation of guest molecules from their pores, challenging. However, an increasing number of publications dealing with the synthesis, structural characterization and properties of ADC-based CPs and MOFs, disclose ways to tackle this obstacle. In this regard, using mostly room temperature solution synthesis or mechanochemical synthesis, and very rarely solvothermal synthesis, the ADC linker has successfully been used to form one-, two-, and three-dimensional CPs with metal cations from almost all groups of the periodic table of the elements, whereby its carboxylate groups adopt mainly all types of known coordination modes. ADC-based CPs feature properties, including negative thermal expansion, formation of non-centrosymmetric networks, long-range magnetic ordering, and solid-state polymerization. The first ADC-based microporous MOFs were obtained with Ce(IV), Hf(IV) and Zr(IV), in which the presence of the –C[triple bond, length as m-dash]C– triple-bond within their backbone results in high hydrophilicity, high CO2 adsorption capacity and enthalpy, as well as the uptake of halogen vapors. This discloses the potential of ADC-MOFs for gas storage/separation and water adsorption-based applications. Furthermore, H2ADC/ADC was discovered to undergo facile in situ hydrohalogenation to yield halogen-functionalized fumarate-based CPs/MOFs. This review surveys investigations on ADC-based coordination polymers and metal–organic frameworks, and is intended to stimulate interest on this linker in chemists working in the fields of crystal chemistry or materials science.

Graphical abstract: Acetylenedicarboxylate as a linker in the engineering of coordination polymers and metal–organic frameworks: challenges and potential

Article information

Article type
Feature Article
Submitted
10 5 2022
Accepted
12 7 2022
First published
13 7 2022
This article is Open Access
Creative Commons BY license

Chem. Commun., 2022,58, 8900-8933

Acetylenedicarboxylate as a linker in the engineering of coordination polymers and metal–organic frameworks: challenges and potential

T. J. Matemb Ma Ntep, V. K. Gramm, U. Ruschewitz and C. Janiak, Chem. Commun., 2022, 58, 8900 DOI: 10.1039/D2CC02665A

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