Synthetic, cyclic voltammetric, structural, EPR, and UV-Vis spectroscopic studies of thienyl-containing meso-A(2)B-cor(Cr(V)=O) systems: consideration of three interrelated molecular detection modalities.

We report eight new A(2)B-type (M(n+)) corrolate compounds (two structural studies) that include the oxo[5,15-bis(pentafluorophenyl)-10-R-corrolatochromium(V)] [R = 2-/3-thienyl (1a/2a), 3-thianaphthyl (3a)] species. The first examples of meso-A(2) (thienyl)- and Cr-A(2)B-corrole types are represented herein. Characterization includes cyclic voltammetry, electron paramagnetic resonance, 2D ((1)H and (13)C) NMR, and UV-vis spectroscopy, mass spectrometry, and elemental analysis. Compounds 1a-3a have enabled analyte binding capacity studies. [Cu(2+)...O=Cr(cor)] binding represents a new selective mode of corrole-based detection, whereas free-base A(2)B-corroles exhibited limited M(n+) selectivity. The 10-position substitution affects optical profiles in analyte titrations. A limited amount of PPh(3) O-atom uptake from [O=Cr(cor)] was also demonstrated.