Structure and Photophysics of Indigoids for Singlet Fission: Cibalackrot

Ryerson, Joseph L.; Zaykov, Alexandr; Aguilar Suarez, Luis E.; Havenith, Remco W. A.; Stepp, Brian R.; Dron, Paul I.; Kaleta, Jirí; Akdag, Akin; Teat, Simon J.; Magnera, Thomas F.; Miller, John R.; Havlas, Zdenek; Broer, Ria; Faraji, Shirin; Michl, Josef; Johnson, Justin C.

doi:10.1063/1.5121863

Title: Structure and Photophysics of Indigoids for Singlet Fission: Cibalackrot

Journal Article · Thu Nov 14 00:00:00 EST 2019 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5121863· OSTI ID:1572370

Ryerson, Joseph L. ^[1]; Zaykov, Alexandr ^[2]; Aguilar Suarez, Luis E. ^[3];

^[3]; Stepp, Brian R. ^[4]; Dron, Paul I. ^[4]; Kaleta, Jirí ^[5]; Akdag, Akin ^[4]; Teat, Simon J. ^[6]; Magnera, Thomas F. ^[4];

^[7]; Havlas, Zdenek ^[5];

^[3]; Faraji, Shirin ^[3];

^[8];

^[9]

Univ. of Colorado, Boulder, CO (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Czech Academy of Sciences, Prague (Czech Republic); Univ. of Chemistry and Technology Prague (Czech Republic)
Univ. of Groningen (Netherlands)
Univ. of Colorado, Boulder, CO (United States)
Czech Academy of Sciences, Prague (Czech Republic)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Univ. of Colorado, Boulder, CO (United States); Czech Academy of Sciences, Prague (Czech Republic)
National Renewable Energy Lab. (NREL), Golden, CO (United States)

We report an investigation of structure and photophysics of thin layers of cibalackrot, a sturdy dye derived from indigo by double annulation at the central double bond. Evaporated layers contain up to three phases, two crystalline and one amorphous. Relative amounts of all three have been determined by a combination of X-ray diffraction and FT-IR reflectance spectroscopy. Initially, excited singlet state rapidly produces a high yield of a transient intermediate whose spectral properties are compatible with charge-transfer nature. This intermediate more slowly converts to a significant yield of triplet, which, however, does not exceed 100% and may well be produced by intersystem crossing rather than singlet fission. The yields were determined by transient absorption spectroscopy and corrected for effects of partial sample alignment by a simple generally applicable procedure. Formation of excimers was also observed. In order to obtain guidance for improving molecular packing by a minor structural modification, calculations by a simplified frontier orbital method were used to find all local maxima of singlet fission rate as a function of geometry of a molecular pair. The method was tested at 48 maxima by comparison with the ab initio Frenkel-Davydov exciton model.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); National Renewable Energy Laboratory (NREL), Golden, CO (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Univ. of Colorado, Boulder, CO (United States)

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

Grant/Contract Number:: AC02-05CH11231; AC36-08GO28308; SC0007004; 15-19143S; 19-22806S; 15CSER73

OSTI ID:: 1572370

Alternate ID(s):: OSTI ID: 1579318; OSTI ID: 1580411; OSTI ID: 1607552; OSTI ID: 1688405

Report Number(s):: BNL-212254-2019-JAAM; NREL/JA-5900-74490

Journal Information:: Journal of Chemical Physics, Vol. 151, Issue 18; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 32 works

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Title: Structure and Photophysics of Indigoids for Singlet Fission: Cibalackrot

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