meso-Methyl BODIPY Photocages: Mechanisms, Photochemical Properties, and Applications

Abstract

meso-methyl BODIPY photocages have recently emerged as an exciting new class of photoremovable protecting groups (PPGs) that release leaving groups upon absorption of visible to near-infrared light. In this Perspective, we summarize the development of these PPGs and highlight their critical photochemical properties and applications. We discuss the absorption properties of the BODIPY PPGs, structure−photoreactivity studies, insights into the photoreaction mechanism, the scope of functional groups that can be caged, the chemical synthesis of these structures, and how substituents can alter the water solubility of the PPG and direct the PPG into specific subcellular compartments. Applications that exploit the unique optical and photochemical properties of BODIPY PPGs are also discussed, from wavelength-selective photoactivation to biological studies to photoresponsive organic materials and photomedicine.

Record release of tetramethylguanidine using a green light activated photocage for rapid synthesis of soft materials

“…, halides and acetate). 37 The nomenclature adopted herein is BODIPY-Z-X-R , where Z is F or Me , X is H or Br , and R is the meso -methyl cargo ( e.g. , TMG ).…”

Non-covalent attachment of BODIPY-caged amines to graphene and their localized photocleavage

“…A relatively recent but extensively studied addition to the field of PPGs is boron-dipyrromethene (BODIPY)-based PPGs, which have shown to be biocompatible, easily tuneable, and highly selective in their photocleavage range. 14–21 Additionally, they can cleave in optical ranges that are less harmful to living cells, such as the green and red-light regions. Further, BODIPY PPGs can be used to cap a wide range of cargo, including primary amines, such as dopamine and histamine, and carboxylic acids, such as nitrophenylacetic acid.…”

“…Further, recent studies have demonstrated that while photocleavage of similarly-structured BODIPY-based PPGs in air and aerated solutions results in a reduced quantum yield, photocleavage still proceeds. 19,20…”

Access to isoindole-derived BODIPYs by an aminopalladation cascade

“…14 Furthermore, they have been used as efficient photosensitizers, 15,16 photocatalysts 17,18 and photocages. [19][20][21][22][23][24] BODIPYs are also considered as potential candidates for circularly polarized luminescence. 25 Classically, dyes of the BODIPY family are built up by formation of a dipyrromethene through condensation and oxidation chemistry followed by the insertion of the chelating BF 2 unit via BF 3 ÁOEt 2 .…”