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.

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.