Photophysical and Photochemical Processes of Excited Singlet and Triplet [3_n]Cyclophanes (n = 2–6) Studied by Emission Measurements and Steady-State and Laser Flash Photolyses

Abstract

Photophysical and photochemical features of [3n]cyclophanes (3nCPs) (n = 2-6) in solution were investigated by emission and transient absorption measurements. The studied 3nCPs show excimer fluorescence without locally excited fluorescence whereas some of them emit excimer phosphorescence in rigid glass at 77 K. The probability of excimeric phosphorescence from transannular π-electron systems was shown to strictly depend on the symmetric molecular structures. A feature of intersystem crossing from an excimeric fluorescence state to the excimeric triplet state was observed. Transient absorption spectra obtained upon laser flash photolysis of 3nCP revealed formation of the triplet excimer states. Triplet sensitization of 33CP using xanthone as the sensitizer demonstrated formation of triplet 33CP via triplet energy transfer whereas from the xanthone ketyl radical formation, it was inferred that triplet xanthone undergoes H atom abstraction from 32CP, providing a benzylic 32CP radical as the counter species. Based on kinetic and spectroscopic data obtained upon laser flash photolysis, differences in photochemical reactions of triplet xanthone between 32CP and 33CP were discussed.

Direct Observation of a Triplet-State Absorption-Emission Conversion in a Fullerene-Functionalized Pt(II) Metallacycle

“…Since the first observation of excimer fluorescence from pyrene, several studies have been performed to understand the nature of singlet and triplet excimers by various spectroscopic techniques, such as steady-state absorption and emission spectra and time-resolved transient absorption spectra. − Previous studies have shown that excimers dissipate the excitation energy and usually increase nonradiative transition . Recently, the systems have been reported to show new roles, such as enhancing phosphorescence quantum yield and facilitating singlet fission , and electron transfer .…”