Guest and solvent modulated photo-driven charge separation and triplet generation in a perylene bisimide cyclophane

Spenst, Peter; Young, Ryan M.; Wasielewski, Michael R.; Wurthner, Frank

doi:10.1039/c6sc01574c

Title: Guest and solvent modulated photo-driven charge separation and triplet generation in a perylene bisimide cyclophane

Journal Article · Wed May 18 00:00:00 EDT 2016 · Chemical Science

DOI:https://doi.org/10.1039/c6sc01574c· OSTI ID:1434679

Spenst, Peter ^[1]; Young, Ryan M. ^[2]; Wasielewski, Michael R. ^[2]; Wurthner, Frank ^[1]

Univ. Wurzburg, Wurzburg (Germany)
Northwestern Univ., Evanston, IL (United States)

Cofacial positioning of two perylene bisimide (PBI) chromophores at a distance of 6.5 Å in a cyclophane structure prohibits the otherwise common excimer formation and directs photoexcited singlet state relaxation towards intramolecular symmetry-breaking charge separation (τ_CS = 161 ± 4 ps) in polar CH₂Cl₂, which is thermodynamically favored with a Gibbs free energy of ΔG_CS = –0.32 eV. The charges then recombine slowly in τ_CR = 8.90 ± 0.06 ns to form the PBI triplet excited state, which can be used subsequently to generate singlet oxygen in 27% quantum yield. This sequence of events is eliminated by dissolving the PBI cyclophane in non-polar toluene, where only excited singlet state decay occurs. In contrast, complexation of electron-rich aromatic hydrocarbons by the host PBI cyclophane followed by photoexcitation of PBI results in ultrafast electron transfer (<10 ps) from the guest to the PBI in CH₂Cl₂. As a result, the rate constants for charge separation and recombination increase as the guest molecules become easier to oxidize, demonstrating that charge separation occurs close to the peak of the Marcus curve and the recombination lies far into the Marcus inverted region.

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Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: FG02-99ER14999

OSTI ID:: 1434679

Journal Information:: Chemical Science, Vol. 7, Issue 8; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 59 works

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