title: Thermally-Activated, Delayed Fluorescence in O,B,O- and N,B,O-Strapped Boron Dipyrromethene Derivatives.
abstract: A small series of boron dipyrromethene (BODIPY) dyes has been synthesized whereby the boron atom is constrained in a five-membered ring formed from either o-dihydroxypyridine or o-aminophenol. In the latter case, the amino group has been converted into the corresponding amide derivative so as to curtail the possibility for light-induced charge transfer from strap to BODIPY. These compounds are weakly emissive in fluid solution but cleavage of the strap, by treatment with a photoacid generator, restores strong fluorescence. Surprisingly, the same compounds remain weakly fluorescent in a rigid glass at 80 K where light-induced charge transfer is most unlikely. In fluid solution, the fluorescence quantum yield increases with increasing temperature due to a thermally activated step but does not correlate with the thermodynamics for intramolecular charge transfer. It is proposed that the strap causes rupture of the potential energy surface for the excited state, creating traps that provide new routes by which the wave packet can return to the ground state. Access to the trap from the excited state is reversible, leading to the delayed emission. Analysis of the temperature dependent emission intensities allows estimation of the kinetic parameters associated with entering and leaving the trap.
authors.affiliation: Molecular Photonics Laboratory, ‡School of Chemistry, Bedson Building, Newcastle University , Newcastle upon Tyne NE1 7RU, United Kingdom.
authors.forename: Patrycja
authors.initials: P
authors.lastname: Stachelek
authors.affiliation: Molecular Photonics Laboratory, ‡School of Chemistry, Bedson Building, Newcastle University , Newcastle upon Tyne NE1 7RU, United Kingdom.
authors.forename: Abdulrahman A
authors.initials: AA
authors.lastname: Alsimaree
authors.affiliation: Molecular Photonics Laboratory, ‡School of Chemistry, Bedson Building, Newcastle University , Newcastle upon Tyne NE1 7RU, United Kingdom.
authors.forename: Rua B
authors.initials: RB
authors.lastname: Alnoman
authors.affiliation: Molecular Photonics Laboratory, ‡School of Chemistry, Bedson Building, Newcastle University , Newcastle upon Tyne NE1 7RU, United Kingdom.
authors.forename: Anthony
authors.identifier: http://orcid.org/0000-0003-0679-2232
authors.initials: A
authors.lastname: Harriman
authors.affiliation: Molecular Photonics Laboratory, ‡School of Chemistry, Bedson Building, Newcastle University , Newcastle upon Tyne NE1 7RU, United Kingdom.
authors.forename: Julian G
authors.initials: JG
authors.lastname: Knight