Synthesis and crystal structure of core-modified benziporphyrin: thia-p-benziporphyrin

The core-modified 5,20-phenyl-10,15-tolyl-thia-p-benziporphyrin (SBzP) can be prepared from the condensation of 1,4-bis(α-hydroxyl-benzyl)benzene with 5,10-ditolyl-16-thia-5,10,15,17-tetrahydrotripyrrin using BF₃·OEt₂ as catalyst. Spectroscopic studies suggest an aromatic macrocycle with a rapid flipping phenylene ring. SBzP exhibits a tilted phenylene ring and crystal packing shows dimeric structure with two SBzP rings linked by hydrogen bonding and π-π interaction. TFA acidified SBzPH₂²⁺ has a saddle-shaped dication porphyrin ring with two solvated trifluoroacetate and two solvated trifluoroacetic acid linked by hydrogen bondings.