2,5‐Thienylene‐Strapped Bicyclic and Tricyclic Expanded Porphyrins

Abstract

An [18]thiaporphyrin[36]dithiaoctaphyrin‐[18]thiaporphyrin tricyclic macrocycle, fused through the 2,5‐thienylene bridging moiety, was isolated during the preparation of 2,5‐thienylene‐strapped [26]hexaphyrin containing o‐dichlorophenyl groups as meso substituents. The spectroscopic data of the 2,5‐thienylene‐strapped [26]hexaphyrin verified contributions of aromaticity from ring currents of both the [18]thiaporphyrin and the [26]hexaphyrin. The crystal structure of the tricyclic macrocycle revealed a distorted [36]dithiaoctaphyrin central core with two [18]thiaporphyrin sidewheels oriented nearly perpendicular to the mean‐plane of dithiaoctaphyrin, implying the existence of independent π‐conjugated systems. Both the absorption maximum at 441 nm and the chemical shifts in the 1H NMR spectrum of the tricyclic macrocycle are dominated by diatropic ring currents of two aromatic [18]thiaporphyrin sidewheels.

Corroles and Hexaphyrins: Synthesis and Application in Cancer Photodynamic Therapy

“…The change in the polarization results in electronic perturbations of the π conjugation. In this regard, chalcogen-substituted hexaphyrins have been synthesized [ 103 , 104 , 105 , 106 , 107 , 108 ], some of them having been explored as NIR photodynamic therapy agents [ 109 ], and others such as dithiabronzaphyrin 130 [ 108 ] show intense absorption and fluorescence in the NIR region, opening the way for their use in biological applications.…”

2,5‐Thienylene‐Strapped [26]Hexaphyrin as Multifunctional Chemosensor for Hg2+, Cu2+, and F− Ions

“…5,10,15,20‐Tetrakis(2,6‐dichlorophenyl)‐21‐thiaporphyrin ( S1 ) and 2,5‐thienylene‐strapped tetrakis(2,6‐dichlorophenyl)‐[26]hexaphyrin ( S2 ) were synthesized following the methods reported in the literature from the condensation of different stochiometric of tripyrromethane and thiophene diol in the presence of Lewis acid following with oxidation reaction by 2,3‐dichloro‐5,6‐dicyano‐ p ‐benzoquinone [23,24] . The isolated pure compounds from column chromatography were character by various spectroscopic methods such as NMR, ESI‐MS, IR, and UV–vis [25,26] …”

“…The reaction mixture was purified by silica gel chromatography using neat CH 2 Cl 2 to obtain the solution of 2 . After concentration, 2 was recrystallization from CH 2 Cl 2 /n‐hexane to give brown crystals (66 mg, 21 %) [23] . And 5,10,15,20‐tetrakis(2,6‐dichlorophenyl)‐21‐thiaporphyrin( S1 ) was synthesized according to the reported Literature [36] …”