Synthesis, Spectral, Redox, and Sensing Studies of β-Dicyanovinyl-Appended Corroles and Their Metal Complexes

Abstract

A new family of β-dicyanovinyl (DCV)-appended corroles represented as MTPC(MN) (where M = 3H, Cu, Ag, and Co(PPh 3 ) and MN = malononitrile and TPC = 5,10,15-triphenylcorrole) were synthesized starting from the free base mono β-formyl corrole, H 3 TPC(CHO), and characterized along with their respective MTPC(CHO) and MTPC complexes as to their spectroscopic and electrochemical properties in nonaqueous media. Comparisons between the two series of corroles demonstrate a pronounced substituent effect of the β-DCV group on the physicochemical properties making the MTPC(MN) derivatives substantially easier to reduce and more difficult to oxidize than the formyl or unsubstituted corroles. In addition, the colorimetric and spectral detection of 11 different anions (X) in the form of tetrabutylammonium salts (TBAX, X

Inverse Hypercorroles

“…b The MOs are visually depicted in Figure 6. formyl-, 45 dicyanovinyl-and dicyanobutadienyl-metallocorroles 46,47 in which strong NIR absorptions primarily reflect an extension of the corrole's conjugation, with varying contributions of corrole-to-substituent charge transfer character.…”

“…Such transitions reflect a clean LUMO switch in these systems (relative to other meso -triarylcorroles and tetraarylporphyrins), from macrocycle- to meso -aryl-based, as a result of the relatively weak electronic coupling between the macrocycle and the significantly twisted (i.e., out-of-plane) aryl substituents. These systems may be contrasted with β-formyl-, dicyanovinyl- and dicyanobutadienyl- metallocorroles , in which strong NIR absorptions primarily reflect an extension of the corrole’s conjugation, with varying contributions of corrole-to-substituent charge transfer character.…”

Highly Efficient β‐Functionalized Oxidomolybdenum(V) Corroles for Catalytic Oxidative Bromination of Phenols at Room Temperature

“…[71,72] Mo-1 was reacted with malononitrile (MN) in dichloromethane using basic Al 2 O 3 as a base and stirred at ambient temperature for 4 h, resulting in Mo-2 in 90 % yield (Scheme 1). [73] Both complexes were characterized using mass spectrometry (Figures S1-S2), electrochemistry and EPR, FT-IR and UV-vis spectroscopic techniques.…”

Panchromatic and Perturbed Absorption Spectral Features and Multiredox Properties of Dicyanovinyl- and Dicyanobutadienyl-Appended Cobalt Corroles

“…We have employed Vilsmeier–Haack formylation followed by Knoevenagel condensation to generate π-extended cobalt corroles with one or two strong electron-withdrawing DCV and DCBD acceptors. Earlier, Vilsmeier–Haack formylation has been utilized on free base, ReO, gold, gallium, and aluminum corroles. − Paolesse and co-workers reported various Vilsmeier reactions with 3-DMA/POCl 3 on the free base, copper, gallium, and cobalt corroles to introduce the acroleyl group on the corrole ring. We have formylated triphenylphosphine­[5,10,15-tritolylcorrolato]­cobalt corrole ( (Cor)­Co ) via Vilsmeier–Haack reaction using DMF/POCl 3 .…”