Synthesis of Pyridine-Containing Crowned Fused Expanded Porphyrins.

Abstract

New examples of nonaromatic fused expanded porphyrins containing both pyridine and crown ether moiety as a part of macrocyclic framework were synthesized by condensing pyridine based pentapyrrane with polyether-based diol in CH2 Cl2 in the presence of one equivalent of BF3 ⋅ OEt2 under inert conditions followed by oxidation with DDQ in open air. The condensation was expected to form pyridine-containing crowned expanded porphyrins but resulted in the formation of fused crowned expanded porphyrins due to intramolecular fusion of two pyrrole nitrogens with two adjacent inverted thiophene carbons as revealed by X-ray crystallography obtained for one of the macrocycle. HRMS and NMR studies supported the formation of fused crowned pyridine containing expanded porphyrins, and the macrocycles showed simple, well-resolved NMR spectra where all resonances were identified easily by 2D NMR spectroscopy. The macrocycles exhibited typical nonaromatic absorption features and showed one broad band with peak maxima at 535 nm and one or two shoulder bands in the higher energy region. The protonation studies resulted in clear colour change from purple to blue and absorption bands experienced bathochromic shifts with a broad band at 662 nm which was extended up to 800 nm. The electrochemical studies revealed that the macrocycles were easier to oxidize but difficult to reduce. DFT studies indicated that the macrocycle attains a very puckered and distorted 'U' shaped structure owing to the flexibility of the crown ether chain and TD-DFT studies corroborated experimental results. The preliminary studies indicated that the macrocycles could be used as colorimetric optical sensor for the detection of Cu2+ ion.