Formation of 8-RS-BODIPYs via direct substitution of 8-MeS-BODIPY by RSH (R = Et, Pr, Bu, tBu, n-C12H25, C6H5, p-MeC6H4, p-MeOC6H4, and 2,6-Me2C6H3)

Abstract

Reactions between 8-RS-BODIPY (R = Me, 1) and alkyl and aryl thiols were readily accomplished in dichloromethane to provide a synthetic pathway to a range of new 8-organothio-BODIPYs in good yield. The new alkyl 8-RS-BODIPYs (R = Et, 2; Pr, 3; Bu, 4; tBu, 5; n-dodecyl, 6) exhibit absorption and emission properties essentially unchanged from those of 1 whereas the arylthio analogs (R = Ph, 7; 2,6-Me2C6H3, 8; p-MeC6H4, 9; p-MeOC6H4, 10) exhibit no fluorescence with the exception of 7, and then only in hexane. In common with other related 8-substituted BODIPYs, the new 8-alkylthio-BODIPY dyes show decreasing fluorescence intensity as solvent polarity increases. Compounds 2, 3, 7, and 8 were characterized via single-crystal X-ray analysis; the alkyl derivatives 2 and 3 exhibited planar BODIPY cores with co-planar organothio- substituents whereas the aryl derivatives exhibited both BODIPY core deformation and significant twisting about the S–C (8) bond removing co-planarity between the aryl group and the distorted BODIPY core. These deformations coincide with the significantly reduced emission properties.