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.