Subtle structural variation in copper metal-organic frameworks: syntheses, structures, magnetic properties and catalytic behaviour?

Dalton Transactions Pub Date: 2008-10-22 DOI: 10.1039/B807063F

Abstract

Two new copper metal-organic frameworks containing 5-nitro-1,3-benzenedicarboxylate (5-nbdc) have been prepared from the reaction between Cu(NO3)2·3H2O and H2(5-nbdc) in DMF at different temperatures. Single crystal X-ray structures of {[Cu2(5-nbdc)2(DMF)2]·2DMF}∞ (1) and {[Cu2(5-nbdc)2(DMF)2]·3?DMF}∞ (2) revealed similar sheet structures, containing triangular and hexagonal pores, but differences in the stacking of the sheets. Magnetic measurements on 1 and 2 are consistent with antiferromagnetic dimers containing a small quantity of paramagnetic impurity. The desolvated forms of 1 and 2 were applied as Lewis acid catalysts in the acetylation of methyl 4-hydroxybenzoate. When the reaction between Cu(NO3)2·3H2O and H2(5-nbdc) was carried out in a mixture of DMF and water, the reaction gave metallomacrocycles of formula [Cu6(5-nbdc)6(H2O)12(DMF)6] (3). These assemble through hydrogen-bonding interactions to form a gross structure in which the macrocycle pores align into channels. The reaction between Cu(NO3)2·3H2O and 5-methylsulfanylmethyl-1,3-benzenedicarboxylic acid, H2(5-msbdc), in DMF-water gave {[Cu2(5-msbdc)2(OH2)2]·3DMF}∞ (4), which contains similar sheets to those in 1 and 2, whereas the reaction with 5-amino-1,3-benzenedicarboxylic acid, H2(5-abdc), gave {[Cu2(5-abdc)2(DMF)2]}∞ (5), which has a previously reported network based on sheets containing rhombohedral pores. The reaction between Cu(NO3)2·3H2O and 2-methoxy-1,3-benzenedicarboxylic acid, H2(2-mbdc), in DMF gave [Cu2(2-mbdc)2(DMF)2] (6). The presence of the substituent in the 2-position removes the co-planarity of the carboxylate groups, and the sheet structure adopted by 6 contains rhomboidal pores.

Graphical abstract: Subtle structural variation in copper metal-organic frameworks: syntheses, structures, magnetic properties and catalytic behaviour
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