Highly reducible π-extended copper corroles

摘要: Di- and octa-phenylethynyl (PE) substituted π-extended copper corroles were synthesized characterized as to their structural, electrochemical spectroscopic properties. The addition of two or eight PE groups the β-pyrrole positions corrole results in dramatic red shifts electronic absorption spectra new reductions which are not seen for parent compound lacking substituents. CuCor(PE)8 is reduced four reversible one-electron transfer steps give derivatives [CuCor(PE)8]n− where n = 1, 2, 3 4. Variable temperature 1H NMR EPR measurements carried out suggest that octa- di-PE Cu-corroles can both be described an antiferromagnetically coupled CuII cation radical equilibrium with a triplet state, possibly due lower singlet–triplet energy gap compared 1 2 at room temperature. oxidized one electron species exhibited characteristics Cu(II) corroles. products generated first each by thin-layer spectroelectrochemistry, thus providing insights into how UV-vis highly vary function number overall charge on molecule. singly also chemically CH3CN shown have UV-visible almost identical obtained electroreduction electrooxidation PhCN THF containing 0.1 M tetrabutylammonium perchlorate.