Manipulating Charge‐Transfer States in BODIPYs: A Model Strategy to Rapidly Develop Photodynamic Theragnostic Agents. Issue 3 (17th December 2019)

• Record Type: Journal Article
• Authors: Jiménez, Josué; Prieto‐Montero, Ruth; Maroto, Beatriz L.; Moreno, Florencio; Ortiz, María J.; Oliden‐Sánchez, Ainhoa; López‐Arbeloa, Iñigo; Martínez‐Martínez, Virginia; de la Moya, Santiago
• Is Part Of: Chemistry. Volume 26:Issue 3(2020)
• Page Start: 601
• Page End: 605
• Publication Date: 2019-12-17
• Subjects: charge transfer -- photodynamic therapy -- singlet oxygen -- theragnosis -- triplet modulation; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201904257
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: On the basis of a family of BINOL (1, 1′‐bi‐2‐naphthol)‐based O ‐BODIPY (dioxyboron dipyrromethene) dyes, it is demonstrated that chemical manipulation of the chromophoric push–pull character, by playing with the electron‐donating capability of the BINOL moiety (BINOL versus 3, 3'‐dibromoBINOL) and with the electron‐acceptor ability of the BODIPY core (alkyl substitution degree), is a workable strategy to finely balance fluorescence (singlet‐state emitting action) versus the capability to photogenerate cytotoxic reactive oxygen species (triplet‐state photosensitizing action). It is also shown that the promotion of a suitable charge‐transfer character in the involved chromophore upon excitation enhances the probability of an intersystem crossing phenomenon, which is required to populate the triple state enabling singlet oxygen production. The reported strategy opens up new perspectives for rapid development of smarter agents for photodynamic theragnosis, including heavy‐atom‐free agents, from a selected organic fluorophore precursor. Abstract : Chemically tuning charge‐transfer states (CTSs) in BODIPYs (boron dipyrromethenes) is revealed as workable strategy to modulate the population of triplet excited states in monochromophoric dyes focused to photodynamic theragnosis (PDT aided by fluorescence bioimaging). The strategy can be easily extended to different systems and triplet applications beyond PDT (in scheme: CT=charge transfer, ISC=intersystem crossing).