Synthesis, optical, and electrochemical properties, and theoretical calculations of BODIPY containing triphenylamine

Abstract

The boron dipyrromethene (BODIPY) triads consisting of two triphenylamine units as electron donor (D) and BODIPY core as electron acceptor (A; B3, and B4) have been synthesized using facile palladium cross‐coupling reactions to broaden the absorption of the BODIPY dyes. All dyes and intermediates were characterized by 1H NMR, 11B NMR, 13C NMR, and 19F NMR spectroscopies, UV–Vis spectroscopy, fluorescence spectroscopy, cyclic voltammetry, and time‐dependent density functional theory calculations. It was found that an increase in conjugation to the BODIPY core systematically extended the absorption and emission wavelength maxima. As a consequence, B4 containing the D–π–A–π–D structure, exhibited the longest absorption and emission maxima at 597 and 700 nm, respectively, with 1.8 eV in optical bandgap. The 96 nm red‐shifted absorption of B4 as compared to the unsubstituted BODIPY (B1) indicated the effective electronic communication between triphenylamine and BODIPY. This suggested that the proper alignment of triphenylamine and BODIPY triad could lead to broader absorption and suitable low energy bandgap. Furthermore, the molecular modeling has been employed to analyze the electronic and optical properties of the dyes. We found that the optical, electrochemical, and theoretical bandgaps of all dyes were in good agreement.

Asymmetric Dipyrrin and F-BODIPYs Conjugated to Terminal Alkynes and Alkenes

“…Particularly appealing is the incorporation of an acetelyne substituent on the β-positions of the dipyrrinato ligand with the goal of both extending πconjugation and introducing a functional handle for linkage to other moieties. [29][30][31][32][33][34][35][36][37][38][39][40][41][42][43] Despite the large body of work concerning the synthesis and the reactions of alkene-substituted F-BODIPYs, systems substituted with terminal alkenes are scarce. 44 In an ongoing effort to synthesize new dipyrrole-based dyes and investigate their photochemical properties and reactivity, [45][46][47][48][49][50] we targeted the meso-H asymmetric dipyrrin 1 (Scheme 1), featuring a terminal alkyne directly conjugated to the dipyrrinato core, and complexed to -BF 2 to provide the F-BODIPY 4.…”

A Time-Resolved Spectroscopic Investigation of a Novel BODIPY Copolymer and Its Potential Use as a Photosensitiser for Hydrogen Evolution

“…The emission map ( Figure 4B) follows closely the absorption profile of the ground state, indicating coupling of the chromophores responsible for the two lowest energy features in the absorption spectrum to the emissive state. (Wanwong et al, 2016) ( Supplementary Figure 30). d Flourescence quantum yield calculated using 3-pyridine H-BODIPY as a reference standard, where fl = 62% in CH 2 Cl 2 (Banfi et al, 2013), detailed in the experimental section.…”

The effect of co-sensitization methods between N719 and boron dipyrromethene triads on dye-sensitized solar cell performance

“…Materials 4-Iodobenzyl-meso-BODIPY (compound 1) and 4-ethynyltriphenylamine were synthesized according to reported literature. 34 4-Formylphenylboronic acid pinacol ester, Niodosuccinimide, copper iodide, tetrakis(triphenylphosphine) palladium(0) (Pd(PPh 3 ) 4 ), cyanoacetic acid were purchased from Aldrich. Anhydrous sodium sulfate, potassium carbonate, triethylamine, ammonium acetate, and glacial acetic acid were purchased from Fisher.…”