General Route to Symmetric and Asymmetricmeso-CF₃-3(5)-Aryl(hetaryl)- and 3,5-Diaryl(dihetaryl)-BODIPY Dyes

Abstract

A general efficient route to hitherto inaccessible symmetric and asymmetric meso-CF(3)-BODIPY dyes has been developed. The key stages include the reduction of available 2-trifluoroacetylpyrroles to the corresponding alcohols which are further condensed with pyrroles. The method allows the BODIPY with 3(5)aryl(hetaryl) and 3,5-diaryl(hetaryl) substituents to be readily assembled. The BODIPY dyes synthesized fluoresce (Φ(f) = 0.56-1.00) in the 560-680 nm region.

Synthesis and Optical Properties of Difluorobora‐s‐diazaindacene Dyes with Trifluoromethyl meso‐Substituents

“…[13] This approach allows both absorption and emission to be shifted by 100-200 nm towards red. [16] We have concisely reported that the presence of a CF 3 group in the meso-position of the BODIPY core does cause a deep bathochromic shift relative to congeners with other substituents in this position. [16] We have concisely reported that the presence of a CF 3 group in the meso-position of the BODIPY core does cause a deep bathochromic shift relative to congeners with other substituents in this position.…”

“…Very important shifts towards the NIR end of the visible spectra have been recently achieved by introducing a strong electron acceptor such as pentafluorobenzene [14] or CF 3 [15,16] at the meso-position of the BODIPY core, though the asymmetrical representatives with a meso-CF 3 moiety can only be synthesized by using a specific methodology. [16] Despite this progress, synthesis of new meso-CF 3 -BODIPY derivatives with aryl groups remains challenging because the fluorescence maxima of BODIPY strongly depend on the nature of the aryl substituent. [16] Despite this progress, synthesis of new meso-CF 3 -BODIPY derivatives with aryl groups remains challenging because the fluorescence maxima of BODIPY strongly depend on the nature of the aryl substituent.…”

Synthesis and properties of 3-ethynylthiophene containing BODIPY derivatives

“…Numerous aromatic and aliphatic substituents have been used to modify the BODIPY core. Substitution at the 2,6 and 3,5 positions has been widely used to extend conjugation [9][10][11][12]. Substitution at the meso position and boron center does not cause significant shift in absorption and emission spectra [13].…”

Electrochemistry, Electrogenerated Chemiluminescence, and Electropolymerization of Oligothienyl-BODIPY Derivatives

“…[17][18][19] The substitution of heteroaromatic residues, especially in the 3,5 positions, endow to the BODIPYs significant red shifted spectral transitions. [20][21] We have previously demonstrated that 3,5-dithienyl BODIPYs [22][23][24] exhibit comparable red shifted emission with respect to the 3,5-diphenyl analogue. [23][24] There are even fewer examples of oligothiophenes attached to BODIPY derivatives, [25][26][27][28][29] some being those with oligothiophenes attached in the meso position to give donor/acceptor materials.…”

“…[20][21] We have previously demonstrated that 3,5-dithienyl BODIPYs [22][23][24] exhibit comparable red shifted emission with respect to the 3,5-diphenyl analogue. [23][24] There are even fewer examples of oligothiophenes attached to BODIPY derivatives, [25][26][27][28][29] some being those with oligothiophenes attached in the meso position to give donor/acceptor materials. We recently reported the grafting of short conjugated oligothiophene chains to the 3,5 positions of BODIPY derivatives.…”