Unprecedented one-pot sequential thiolate substitutions under mild conditions leading to a red emissive BODIPY dye 3,5,8-tris(PhS)-BODIPY.

The simple reaction of phenylthiol with 8-MeS-BODIPY (1) in dichloromethane was readily accomplished to form 8-PhS-BODIPY (2). If the reaction is performed in THF 3,8-bis(phenylthio)-BODIPY (3) and 3,5,8-tris(phenylthio)-BODIPY (4) are sequentially formed in an unprecedented reaction. This provides a simple new methodology for the introduction of the phenylthio-moiety in the 3- and 5-positions. Alkyl thiols do not form multi-thiolated products under identical conditions, as exemplified using EtSH, where only 8-EtS-BODIPY (5) is formed.