Synthesis, structure, and magnetic properties of bithiophene- and terthiophene-linked manganese metal-organic frameworks.
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, 2-4 are 3D frameworks, and 5 is a 1D chain. Compounds 3 and 4 are isomers, and 3-5 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 1-3 and 5 show antiferromagnetic behavior with typical values of g and J, and 3 exhibits a spin canting transition at 40 K.
Department of Chemistry, University of British Columbia, Vancouver, British Columbia, V6T 1Z1 Canada.
Lyndsey D
LD
Earl
Brian O
BO
Patrick
Michael O
MO
Wolf
D018360:Crystallography, X-Ray; D003998:Dicarboxylic Acids / Q000138:chemical synthesis / Q000737:chemistry; D008280:Magnetics; D059346:Magnets / Q000737:chemistry; D008345:Manganese / Q000737:chemistry*; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013876:Thiophenes / Q000138:chemical synthesis / Q000737:chemistry*
D003998:Dicarboxylic Acids; D009942:Organometallic Compounds; D013876:Thiophenes; D008345:Manganese