Dihydronaphthalene-Fused Boron–Dipyrromethene (BODIPY) Dyes: Insight into the Electronic and Conformational Tuning Modes of BODIPY Fluorophores

Abstract

A new series of boron–dipyrromethene (BDP, BODIPY) dyes with dihydronaphthalene units fused to the β-pyrrole positions (1 a–d, 2) has been synthesised and spectroscopically investigated. All the dyes, except pH-responsive 1 d in polar solvents, display intense emission between 550–700 nm. Compounds 1 a and 1 b with a hydrogen atom and a methyl group in the meso position of the BODIPY core show spectroscopic properties that are similar to those of rhodamine 101, thus rendering them potent alternatives to the positively charged rhodamine dyes as stains and labels for less polar environments or for the dyeing of latex beads. Compound 1 d, which carries an electron-donating 4-(dimethylamino)phenyl group in the meso position, shows dual fluorescence in solvents more polar than dibutyl ether and can act as a pH-responsive “light-up” probe for acidic pH. Correlation of the pK_a data of 1 d and several other meso-(4-dimethylanilino)-substituted BODIPY derivatives allowed us to draw conclusions on the influence of steric crowding at the meso position on the acidity of the aniline nitrogen atom. Preparation and investigation of 2, which carries a nitrogen instead of a carbon as the meso-bridgehead atom, suggests that the rules of colour tuning of BODIPYs as established so far have to be reassessed; for all the reported couples of meso-C- and meso-N-substituted BODIPYs, the exchange leads to pronounced redshifts of the spectra and reduced fluorescence quantum yields. For 2, when compared with 1 a, the opposite is found: negligible spectral shifts and enhanced fluorescence. Additional X-ray crystallographic analysis of 1 a and quantum chemical modelling of the title and related compounds employing density functional theory granted further insight into the features of such sterically crowded chromophores.