Regioselective Stepwise Bromination of [14]Triphyrins(2.1.1) and Their Effects on Structural, Spectral, and Redox Properties.

Abstract

Regioselective stepwise bromination of meso-tetraaryl [14]triphyrins(2.1.1) was explored to investigate the effect of bromine substitution at the β-pyrrole carbons of triphyrin(2.1.1) on the structural, spectral, photophysical, and redox properties. A series of β-monobromo to β-hexabromo triphyrins(2.1.1) 2-7 were synthesized by treating triphyrin(2.1.1) 1 with appropriate equivalents of N-bromosuccinimide at ambient temperature in decent yields. The regiochemistry of bromines in β-brominated triphyrins(2.1.1) 3-5 and 7 was confirmed by X-ray crystallography, and the analysis revealed the effect of bromination of triphyrin(2.1.1) on the structural framework was significant in the case of hexabromotriphyrin(2.1.1) 7 compared to other macrocycles. Absorption spectroscopy showed that stepwise substitution of bromines at β-pyrrole carbons of triphyrin(2.1.1) resulting in bathochromic shifts of absorption bands relative to triphyrin(2.1.1) 1 and hexabromotriphyrin(2.1.1) 7 exhibited absorption bands at longer wavelengths. The redox studies revealed that compounds 2-7 were easier to reduce than triphyrin(2.1.1) 1, and the first reduction potential wave shifted anodically with an increase in the number of bromine substituents at β-pyrrole carbons of triphyrin(2.1.1) 1 from one to six. These structural, spectral, and electrochemical properties were also predicted by density functional theory calculations, and the analysis was consistent with the experimental observations.