Synthesis and characterization of the novel shape-persistent nanosized cavity macrocycle

Abstract

The Friedel–Crafts reaction was employed to prepare the shape-persistent macrocycle ( TPAP) 3 with direct cyclization from three monomers of 2-(4′-(Phenyl(4″-methylphenyl)amino) phenyl)-propan-2-ol ( TPAP), which contains two reactive groups of the t-hydroxyl and the p-proton on the triphenylamine. Under a very low monomer concentration (ca. 1%), the yield of the shape-persistent macrocycle ( TPAP) 3 is up to 34%. FT-IR, NMR, MALDI-TOF and MS were applied to determine the structure of macrocycle. It can be a good candidate as the hole-transporting layer because its photoluminescent spectrum appears no emission peaks in the range of 400–600 nm. The geometry of ( TPAP) 3, optimized by the density functional theory (DFT) calculations using Gaussian03 software at the B3LYP/6-31G(d) level, showed that ( TPAP) 3 possesses an approximately 10 Å diameter and 8.4 Å depth molecular inner cavity. Owing to three nitrogenous lone electron pairs and six conjugated large π bonds of the macrocyclic electron-excessive phenylene almost directing into the cavity, the macrocycle is a big electron-rich donor which may be favorable for selective extraction of special diameter metal ions, high effective and selective catalysis and the formation of 1:1 π-donor–π-acceptor (C60) complexes through the host–guest interactions.