Ultrafast Two-Electron Transfer in a CdS Quantum Dot–Extended-Viologen Cyclophane Complex

Young, Ryan M.; Jensen, Stephen C.; Edme, Kedy; Wu, Yilei; Krzyaniak, Matthew D.; Vermeulen, Nicolaas A.; Dale, Edward J.; Stoddart, J. Fraser; Weiss, Emily A.; Wasielewski, Michael R.; Co, Dick T.

doi:10.1021/jacs.5b13386

Ultrafast Two-Electron Transfer in a CdS Quantum Dot–Extended-Viologen Cyclophane Complex

Journal Article · Mon Apr 25 00:00:00 EDT 2016 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.5b13386· OSTI ID:1387722

Young, Ryan M. ^[1]; Jensen, Stephen C. ^[1]; Edme, Kedy ^[1]; Wu, Yilei ^[1]; Krzyaniak, Matthew D. ^[1]; Vermeulen, Nicolaas A. ^[2]; Dale, Edward J. ^[2]; Stoddart, J. Fraser ^[2]; Weiss, Emily A. ^[1]; Wasielewski, Michael R. ^[1]; Co, Dick T. ^[1]

Northwestern Univ., Evanston, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER)
Northwestern Univ., Evanston, IL (United States)

Time-resolved optical spectroscopies revealmulti-electron transfer from the biexcitonic state of a CdS quantum dot toan adsorbed tetracationic compoundcyclobis(4,4'-(1,4-phenylene)bipyridin-1-ium-1,4-phenylene-bis(methylene))(ExBox⁴⁺)to formboth the ExBox³⁺∙and the doubly reduced ExBox2(+∙)statesfrom a single laser pulse. Electron transfer in the single-exciton regime occurs in 1 ps.At higher excitation powers the second electron transfertakes~5ps, which leadsto a mixture of redox states of the acceptor ligand.The doubly reducedExBox2(+∙)state has a lifetime of ~10 ns, while CdS⁺∙:ExBox³⁺∙recombines with multiple time constants, the longest of which is ~300 μs. The long-lived charge separation and ability to accumulate multiple charges on ExBox⁴⁺ demonstrate the potential of the CdS:ExBox4+complex to serve as a platform for two-electron photocataly-sis.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Camille and Henry Dreyfus Postdoctoral Program in Environmental Chemistry; National Science Foundation (NSF); Ryan Fellowship; International Institute for Nanotechnology (IIN)

Grant/Contract Number:: SC0001059

OSTI ID:: 1387722

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 19 Vol. 138; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Ultrafast Two-Electron Transfer in a CdS Quantum Dot–Extended-Viologen Cyclophane Complex

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