Synthetic, Cyclic Voltammetric, Structural, EPR, and UV−Vis Spectroscopic Studies of Thienyl-Containing <i>meso</i>-A₂B-cor(Cr^VO) Systems: Consideration of Three Interrelated Molecular Detection Modalities

We report eight new A2B-type (Mn+) 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-A2 (thienyl)- and Cr-A2B-corrole types are represented herein. Characterization includes cyclic voltammetry, electron paramagnetic resonance, 2D (1H and 13C) NMR, and UV−vis spectroscopy, mass spectrometry, and elemental analysis. Compounds 1a−3a have enabled analyte binding capacity studies. [Cu2+···OCr(cor)] binding represents a new selective mode of corrole-based detection, whereas free-base A2B-corroles exhibited limited Mn+ selectivity. The 10-position substitution affects optical profiles in analyte titrations. A limited amount of PPh3 O-atom uptake from [OCr(cor)] was also demonstrated.