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Synthesis, Structure, and Magnetic Properties of Bithiophene- and Terthiophene-Linked Manganese Metal–Organic Frameworks

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Department of Chemistry, University of British Columbia, Vancouver, British Columbia, V6T 1Z1 Canada
*E-mail: [email protected]. Phone: (604) 822-1702. Fax: (604) 822-2847.
Cite this: Inorg. Chem. 2013, 52, 17, 10021–10030
Publication Date (Web):August 12, 2013
https://doi.org/10.1021/ic401305c
Copyright © 2013 American Chemical Society
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Abstract

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A series of metal–organic frameworks (MOFs) containing manganese centers and oligothiophene dicarboxylate linkers have been synthesized: [Mn(3PhT2DC)(DMF)0.45(H2O)2.55·1.55DMF]n (1), [Mn6(3HT2DC)6(DMF)3(H2O)5·xDMF·yH2O]n (2), [Mn(T3DC)(H2O)2]n (3), [Mn(T3DC)(H2O)1.5]n (4), and [Mn(Ph2T3DC)(DMF)2]n (5) (H23PhT2DC = 3,3′-diphenyl-2,2-bithiophene-5,5′-dicarboxylic acid; H23HT2DC= 3,3′-dihexyl-2,2′-bithiophene-5,5′-dicarboxylic acid; H2T3DC = 2,2′:5′,2″-terthiophene-5,5″-dicarboxylic acid; H2Ph2T3DC = 3′,4′-diphenyl-2,2′:5′,2″-terthiophene-5,5″-dicarboxylic acid, DMF = N,N-dimethylformamide). Compound 1 exists as a 2D sheet, 24 are 3D frameworks, and 5 is a 1D chain. Compounds 3 and 4 are isomers, and 35 are the first examples of crystallographically characterized terthiophene coordination polymers. In the case of 1, 2, and 5, the extended structure is sensitive to β substitution of the oligothiophene linkers. Compounds 13 and 5 show antiferromagnetic behavior with typical values of g and J, and 3 exhibits a spin canting transition at 40 K.

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Crystallographic data, linker coordination modes, TGA traces for 13 and 5, field dependence on the magnetization of 3, selected tabulated IR data, and crystallographic data in CIF format. This material is available free of charge via the Internet at http://pubs.acs.org.

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