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

Content Provider	Royal Society of Chemistry (RSC)
Author	Wasielewski, Michael R. Würthner, Frank Spenst, Peter Young, Ryan M.
Copyright Year	2016
Abstract	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 (τCS = 161 ± 4 ps) in polar CH2Cl2, which is thermodynamically favored with a Gibbs free energy of ΔGCS = −0.32 eV. The charges then recombine slowly in τCR = 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. 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.
Starting Page	5428
Ending Page	5434
Page Count	7
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	7
Issue Number	8
Journal	Chemical Science
DOI	10.1039/c6sc01574c
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Subscribed
Subject Keyword	Gibbs free energy Singlet oxygen PBI Excimer Toluene Carrier generation and recombination Gibbs Electronvolt Perylene Cyclophane Photoexcitation
Content Type	Text
Resource Type	Article
Subject	Chemistry

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