Synthesis of unsymmetrical 2,3,7,8-tetrabromo meso-5,10,11,16-tetraaryl- triphyrin(2.1.1) and its use in the synthesis of sterically crowded 2,3,5,7,8,10,11,16-octaarylated triphyrin(2.1.1)s

Abstract

Triphyrin(2.1.1) is a 14π aromatic contracted congener of an 18π aromatic porphyrin(1.1.1.1). An unsymmetrical 2,3,7,8-tetrabromo meso-tetraaryl triphyrin(2.1.1) containing four bromides at the β-pyrrole carbons of two out of three pyrrole rings of the triphyrin core was synthesized for the first time in 90% yield by treating meso-tetraaryl triphyrin(2.1.1) with five equivalents of N-bromosuccinimide in 1,2-dichloroethane (DCE) under reflux for 8 h. The X-ray structure revealed that the triphyrin(2.1.1) macrocycle was significantly distorted in 2,3,7,8-tetrabromo meso-tetraaryl triphyrin compared to planar meso-tetraaryl triphyrin. A series of novel sterically crowded 2,3,5,7,8,10,11,16-octaaryl triphyrin(2.1.1)s were synthesized by coupling 2,3,7,8-tetrabromo meso-tetraaryl triphyrin with six different aryl boronic acids under Suzuki–Miyaura coupling conditions. NMR, absorption, electrochemical and theoretical studies revealed that the structure and electronic properties were drastically altered in the 2,3,5,7,8,10,11,16-octaaryl triphyrin(2.1.1) series due to the presence of four additional aryl groups at the β-pyrrole carbons which caused steric crowding at the periphery of the triphyrin core resulting in a decrease in effective π-conjugation in the triphyrin(2.1.1)s.