title: Thiol-Activatable Triplet-Triplet Annihilation Upconversion with Maleimide-Perylene as the Caged Triplet Acceptor/Emitter.
abstract: Efficient thiol-activated triplet-triplet annihilation (TTA) upconversion system was devised with maleimide-caged perylene (Py-M) as the thiol-activatable triplet acceptor/emitter and with diiodoBodipy as the triplet photosensitizer. The photophysical processes were studied with steady-state UV-vis absorption spectroscopy, fluorescence spectroscopy, electrochemical properties, and nanosecond transient absorption spectroscopy. The triplet acceptor/emitter Py-M shows week fluorescence (ΦF = 0.8%), and no upconversion (ΦUC = 0%) was observed. The quenching of fluorescence of Py-M is due to photoinduced electron-transfer (PET) process from perylene to maleimide-caging unit, which quenches the singlet excited state of perylene. The fluorescence of Py-M was enhanced by 200-fold (ΦF = 97%) upon addition of thiols such as 2-mercaptoethanol, and the ΦUC was increased to 5.9%. The unique feature of this thiol-activated TTA upconversion is that the activation is based on addition reaction of the thiols with the caged acceptor/emitter, and no side products were formed. The previously reported cleavage approach gives side products which are detrimental to the TTA upconversion. With nanosecond transient absorption spectroscopy, we found that the triplet excited state of Py-M was not quenched by any PET process, which is different from singlet excited state (fluorescence) of Py-M. The results are useful for study of the triplet excited states of organic chromophores and for activatable TTA upconversion.
authors.affiliation: State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology , E-208 West Campus, 2 Ling-Gong Road, Dalian 116024, P. R. China.
authors.forename: Zafar
authors.initials: Z
authors.lastname: Mahmood
authors.affiliation: State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology , E-208 West Campus, 2 Ling-Gong Road, Dalian 116024, P. R. China.
authors.forename: Jianzhang
authors.initials: J
authors.lastname: Zhao