Indexed by:期刊论文

Date of Publication:2016-01-15

Journal:JOURNAL OF ORGANIC CHEMISTRY

Included Journals:SCIE、EI、PubMed

Volume:81

Issue:2

Page Number:587-594

ISSN No.:0022-3263

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 (Phi(F) = 0.8%), and no upconversion (Phi(UC) = 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 (Phi(F) = 97%) upon addition of thiols such as 2-mercaptoethanol, and the Phi(UC) 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.