Dibenzothiophene Bridged Bis‐Bodipy and Bis‐Metal Dipyrrin Complexes

Abstract

AbstractDibenzothiophene (DBT) bridged bis‐dipyrromethane was synthesized by treating readily available 4,6‐di(p‐formylphenyl) dibenzothophene with pyrrole under acid catalyzed conditions. The DBT bridged bis‐dipyrromethane was further oxidized with DDQ to afford the DBT bridged bis‐dipyrrin which was used as a ligand to prepare DBT bridged bis‐BODIPY, bis‐Ni(II) dipyrrin and bis‐Pd(II) dipyrrin complexes by treating the ligand with BF3 ⋅ Et2O, Ni(acac)2 and Pd(acac)2 respectively under mild reaction conditions. The DBT‐bridged bis‐BODIPY and bis‐metal dipyrrin complexes were thoroughly characterized and studied by HR‐MS, 1D & 2D NMR, absorption, fluorescence, cyclic voltammetry and DFT techniques. The bis‐BODIPY and bis‐Pd(II) dipyrrin showed highly intense absorption band at ~500 nm along with one low intense absorption band at 340 nm whereas the bis‐Ni(II) dipyrrin complex showed slightly broadened blue shifted high intense band at 490 nm along with one additional band at 426 nm. The bis‐BODIPY was fluorescent with fluorescence band at 524 nm and quantum yield of 0.031 whereas bis‐M(II) dipyrrin complexes were nonfluorescent. DFT optimized structures revealed that the BODIPY units are more planar with the dibenzophene moiety in bis‐BODIPY with an angle of ∼5.68°. However, in 3‐Pd and 3‐Ni, the M(II)‐dipyrrin units are much more deviated from the dibenzothiophene plane with an angle of 12.81°–14.23°.