Dicarbatriphyrin(2.1.1) and its Carbacalix[1]Phyrin Analogue: Structure-Property Relationships and Application as a Fe(III) Chemosensor.

Abstract

The investigation of unsaturated or π-conjugated hydrocarbons, particularly within the macrocyclic framework, has garnered significant interest due to their fundamental properties and practical applications. This research focuses on the synthesis and characterization of a novel stable dicarbatriphyrin(2.1.1) which was constructed by amending the [14]triphyrin(2.1.1) framework by, replacing two pyrrole rings with meta-connected phenyl rings and introducing an o-benzene bridge at the C2 position. The structural modification resulted in a saddle-shaped macrocyclic core with negative Gaussian curvature, as confirmed by crystal structure analysis. This unique molecular topology offers acumens into the structure-property relationships in the curved locally π-conjugated contracted porphyrinoids. The macrocycle exhibits fluorescent emission in solution, which is selectively quenched by Fe(III) ions, highlighting its potential as a chemosensor for Fe(III) cations. Additionally, the formation of carbacalix[1]phyrin(2.1.1), a phlorin analogue of dicarbatriphyrin(2.1.1), which exhibits a chair conformation in contrast to the saddle-shaped structure of its oxidized counterpart. Remarkably, the emergence of a mono-pyrrolic calixbenziphyrin marks an unprecedented advancement in the field of calixphyrin chemistry. Moreover, theoretical studies provide strong support for the experimental findings, reinforcing the conclusions drawn from the structural and functional analyses.