Interpenetrated Double Pillared-Layer CoII MOFs with pcu Topology*
In-Hyeok Park A , Yunji Kang A , Eunji Lee A , Anjana Chanthapally B , Shim Sung Lee A C and Jagadese J. Vittal B C
+ Author Affiliations
- Author Affiliations
A Department of Chemistry and Research Institute of Natural Science, Gyeongsang National University, Jinju 52828, South Korea.
B Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 11753, Republic of Singapore.
C Corresponding authors. Email: sslee@gnu.ac.kr; chmjjv@nus.edu.sg
Australian Journal of Chemistry 70(5) 461-467 https://doi.org/10.1071/CH16438
Submitted: 27 July 2016 Accepted: 18 September 2016 Published: 14 October 2016
Abstract
Three double pillared-layer CoII metal–organic frameworks (MOFs) with a pcu topology of a long, conformationally flexible, dipyridyl spacer ligand, 1,4-bis[2-(4-pyridyl)ethenyl]benzene (bpeb), and aromatic dicarboxylates (1,4-benzenedicarboxylate (bdc), 2,6-naphthalenedicarboxylate (ndc), and biphenyl-4,4′-dicarboxylate (bpdc)) have been synthesised and structurally characterised by X-ray crystallography. The MOFs are denoted as [Co2(bpeb)2(bdc)2]·DMF·3H2O (1), [Co2(bpeb)2(ndc)2]·1.75DMF·3.75H2O (2), and [Co2(bpeb)2(bpdc)2]·3.5DMF·4H2O (3). In the dinuclear repeating unit, four carboxylates are bonded to two CoII atoms forming a (4,4) layer structure. The axial positions are occupied by bpeb ligands. Of these, 1 and 2 have 2-fold interpenetration, whereas 3 displays 3-fold interpenetration. The two bpeb space ligands in 1 have trans,trans,trans and trans,cis,trans conformations. In contrast, the bpeb ligands in 2 and 3 have a trans,cis,trans conformation. Although the olefin groups in two adjacent bpeb ligands, as the double pillars in 2 and 3, satisfy the conditions for photo-dimerisation to occur, they are photo-inactive. The conformational changes of bpeb, bonding modes of the dicarboxylates, and pore sizes in these double pillared-layer compounds have been discussed.
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