Universität zu Köln

Ntep, Tobie J. Matemb Ma, Gramm, Verena K., Ruschewitz, Uwe ORCID: 0000-0002-6511-6894 and Janiak, Christoph (2022). Acetylenedicarboxylate as a linker in the engineering of coordination polymers and metal-organic frameworks: challenges and potential. Chem. Commun., 58 (64). S. 8900 - 8934. CAMBRIDGE: ROYAL SOC CHEMISTRY. ISSN 1364-548X

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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 (H(2)ADC) 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=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, H(2)ADC/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.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Ntep, Tobie J. Matemb Ma UNSPECIFIED UNSPECIFIED UNSPECIFIED Gramm, Verena K. UNSPECIFIED UNSPECIFIED UNSPECIFIED Ruschewitz, Uwe UNSPECIFIED orcid.org/0000-0002-6511-6894 UNSPECIFIED Janiak, Christoph UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-666969
DOI:	10.1039/d2cc02665a
Journal or Publication Title:	Chem. Commun.
Volume:	58
Number:	64
Page Range:	S. 8900 - 8934
Date:	2022
Publisher:	ROYAL SOC CHEMISTRY
Place of Publication:	CAMBRIDGE
ISSN:	1364-548X
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language SOLID-STATE POLYMERIZATION; INORGANIC 3D NETWORKS; CRYSTAL-STRUCTURE; NONCENTROSYMMETRIC MATERIALS; MECHANOCHEMICAL SYNTHESIS; HYDROGEN STORAGE; SINGLE-CRYSTAL; BUILDING UNITS; LIGAND DESIGN; PORE-SIZE Multiple languages Chemistry, Multidisciplinary Multiple languages
URI:	http://kups.ub.uni-koeln.de/id/eprint/66696