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. 2022 Oct 1;27(19):6481.
doi: 10.3390/molecules27196481.

Structural Diversity and Carbon Dioxide Sorption Selectivity of Zinc(II) Metal-Organic Frameworks Based on Bis(1,2,4-triazol-1-yl)methane and Terephthalic Acid

Taisiya S Sukhikh  1 , Evgeny Yu Filatov  1 , Alexey A Ryadun  1 , Konstantin A Kovalenko  1 , Andrei S Potapov  1
Affiliations

Structural Diversity and Carbon Dioxide Sorption Selectivity of Zinc(II) Metal-Organic Frameworks Based on Bis(1,2,4-triazol-1-yl)methane and Terephthalic Acid

Taisiya S Sukhikh et al. Molecules. .

Abstract

A three-component reaction between the 1,4-benzenedicarboxylic (terephthalic) acid (H2bdc), bis(1,2,4-triazol-1-yl)methane (btrm) and zinc nitrate was studied, and three new coordination polymers were isolated by a careful selection of the reaction conditions. Coordination polymers {[Zn3(DMF)(btrm)(bdc)3]·nDMF}∞ and {[Zn3(btrm)(bdc)3]·nDMF}∞ containing trinuclear {Zn3(bdc)3} secondary building units are joined by btrm auxiliary linkers into three-dimensional metal-organic frameworks. The coordination polymer {[Zn(bdc)(btrm)]∙nDMF}∞ consists of Zn2+ cations joined by bdc2- and btrm linkers into a two-fold interpenetrated network. Upon activation, MOF [Zn3(btrm)(bdc)3]∞ demonstrated CO2/N2 adsorption selectivity with an ideal adsorbed solution theory (IAST) factor of 21. All three MOF demonstrated photoluminescence with a maximum near 435-440 nm upon excitation at 330 nm.

Keywords: bis(1,2,4-triazol-1-yl)methane; coordination polymers; gas adsorption; gas separation; luminescence; metal–organic frameworks; terephthalic acid.

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Conflict of interest statement

The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

Figures

Scheme 1
Scheme 1
Synthesis conditions for the preparation of coordination polymers 1–3a.
Figure 1
Figure 1
Crystal structure of MOF 1: (a) representation of {Zn3(bdc)3} layer; (b) representation of the layers linked by btrm ligands; (c) representation of framework topology of MOF 1. Hydrogen atoms are omitted for clarity.
Figure 1
Figure 1
Crystal structure of MOF 1: (a) representation of {Zn3(bdc)3} layer; (b) representation of the layers linked by btrm ligands; (c) representation of framework topology of MOF 1. Hydrogen atoms are omitted for clarity.
Figure 2
Figure 2
Crystal structure of MOF 2: (a) representation of {Zn3(bdc)3}; (b) representation of the layers linked by btrm ligands. Hydrogen atoms are omitted for clarity.
Figure 3
Figure 3
Crystal structures of MOFs 3 and 3a: (a) fragment of framework 3, hydrogen atoms are omitted for clarity; (b) relative arrangement of two interpenetrated frameworks in 3 and 3a colored blue and red, one hexagonal ring is filled blue.
Figure 4
Figure 4
Gas adsorption-desorption isotherms: (a) N2 (at 77 K) and CO2 (at 195 K) on MOF 1; (b) CO2 (at 195 K) on MOF 3.
Figure 5
Figure 5
Adsorption-desorption isotherms of N2 and CO2 at 273 K on MOF 1.
Figure 6
Figure 6
Normalized emission (λex = 330 nm) (a) and excitation (b) spectra of btrm ligand and synthesized complexes 1–3.
See this image and copyright information in PMC

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