Issue 13, 2020

Exchange coupled Co(ii) based layered and porous metal–organic frameworks: structural diversity, gas adsorption, and magnetic properties

Abstract

Four new Co(II) based metal–organic frameworks (MOFs) ({[Co3(L)(TDCA)3(DMF)2]n·2nCH3CN}) (1), ({[Co3(L)2(BDCA)3]n·2nCH3CN}) (2), {[Co2(L)2(CA)2]n·4nCH3CN} (3) and {[Co2(L)(OBBA)2]n·3nCH3CN} (4) are synthesized, where L is [4′-(4-methoxyphenyl)-4,2′:6′,4′′-terpyridine], a V-shaped flexible neutral spacer, and the four dicarboxylates are TDCA = thiophene 2,5-dicarboxylic acid, BDCA = benzene 1,4-dicarboxylic acid, CA = (1R,3S)-(+)-camphoric acid and OBBA = 4,4′-oxybisbenzoic acid. Structural analysis reveals that 1 and 2 are two dimensional (2D) layered structures having interesting sql and hxl topologies respectively with trinuclear SBUs (secondary building units). Compound 3 has a 3D structure, whereas 4 has a 2-fold interpenetrated 3D packing structure with a paddlewheel dinuclear SBU and both have pcu topology. Magnetic investigation revealed that 1, 3 and 4 show dominant antiferromagnetic behavior, while 2 shows ferromagnetic interaction at very low temperature. Interestingly 4 shows a sharp decrease in the χMT value from room temperature and this may be because of the direct Co(II)⋯Co(II) interaction. Gas sorption studies reveal that 1, 2 and 3 show surface areas of 11.8 m2 g−1, 8.3 m2 g−1 and 28.5 m2 g−1 respectively and better adsorption behavior for CO2 over CH4, whereas 4 is nonporous in nature due to its 2-fold interpenetrated structure.

Graphical abstract: Exchange coupled Co(ii) based layered and porous metal–organic frameworks: structural diversity, gas adsorption, and magnetic properties

Supplementary files

Article information

Article type
Paper
Submitted
18 Qun 2020
Accepted
27 Nah 2020
First published
28 Nah 2020

Dalton Trans., 2020,49, 4012-4021

Exchange coupled Co(II) based layered and porous metal–organic frameworks: structural diversity, gas adsorption, and magnetic properties

A. K. Kharwar and S. Konar, Dalton Trans., 2020, 49, 4012 DOI: 10.1039/D0DT00211A

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