Synthesis, characterization and coordination chemistry of dibenzofuran derivatives of 1,4,7,10-tetraazacyclododecane

A 1,4-disubstituted dibenzofuran derivative of 1,4,7,10-tetraazacyclododecane (cyclen), L1, has been prepared by the direct reaction of cyclen and chloroacetyldibenzofuran and the mono-substituted derivative, L2, by reaction of chloroacetyldibenzofuran and 1,4,7-tris(t-butoxycarbonyl)-1,4,7,10-tetraazacyclododecane followed by deprotection with trifluoroacetic acid. The ligands were characterized by 1H and 13C NMR spectroscopy, IR spectroscopy and mass spectrometry. The reaction of the 1,4-disubstituted dibenzofuran cyclen, L1, with Cu(ClO4)2·6H2O in methanol yielded crystals of [CuL1](ClO4)2·MeOH·1/2H2O that were suitable for single crystal structural analysis. The X-ray structure confirmed that the 1,4-disubstituted dibenzofuran cyclen had been formed. The copper(II) coordination sphere in the complex cation, [CuL1]2+, is occupied by four nitrogen atoms from the macrocycle and an amide oxygen donor from one dibenzofuran pendant group. As is typical for copper(II)–cyclen complexes, the Cu(II) centre sits above the plane of the macrocycle nitrogen towards the oxygen donor, in this case by 0.5 Å. Fluorescence emission studies indicate that coordination of the macrocycle to either copper(II) or zinc(II) results in a decrease in emission with respect to the emission of the pure ligand.

Mono- and 1,4-bis-dibenzofuran derivatives of 1,4,7,10-tetraazacyclododecane (cyclen) have been prepared via classical condensation reactions. The structure of the copper(II) complex of the 1,4-bis(dibenzofuran) derivative square pyramidal coordination sphere occupied by one amide oxygen binds and four macrocycle nitrogens. Addition of Cu2+ and Zn2+ to either ligand was found to quench the emission of the dibenzofuran fluorophore.Figure optionsDownload as PowerPoint slide