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

Abstract

Here, 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. Here, 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.

Authors:
 [1];  [2];  [3]; ORCiD logo [3];  [4];  [4];  [5];  [4];  [6];  [4]; ORCiD logo [7];  [5]; ORCiD logo [3];  [3]; ORCiD logo [8]; ORCiD logo [9]
  1. Univ. of Colorado, Boulder, CO (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. Czech Academy of Sciences, Prague (Czech Republic); Univ. of Chemistry and Technology Prague (Czech Republic)
  3. Univ. of Groningen (Netherlands)
  4. Univ. of Colorado, Boulder, CO (United States)
  5. Czech Academy of Sciences, Prague (Czech Republic)
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  7. Brookhaven National Lab. (BNL), Upton, NY (United States)
  8. Univ. of Colorado, Boulder, CO (United States); Czech Academy of Sciences, Prague (Czech Republic)
  9. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of Colorado, Boulder, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1572370
Alternate Identifier(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 ID: ISSN 0021-9606
Grant/Contract Number:  
AC02-05CH11231; AC36-08GO28308; SC0007004; 15-19143S; 19-22806S; 15CSER73
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 18; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Electron transfer; radiation chemistry; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; sample handling; excitons; spectral phenomena and properties; photochemistry; x-ray diffraction; reflectance spectroscopy; transient-absorption spectroscopy

Citation Formats

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, and Johnson, Justin C. Structure and Photophysics of Indigoids for Singlet Fission: Cibalackrot. United States: N. p., 2019. Web. doi:10.1063/1.5121863.
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. Structure and Photophysics of Indigoids for Singlet Fission: Cibalackrot. United States. doi:10.1063/1.5121863.
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, and Johnson, Justin C. Thu . "Structure and Photophysics of Indigoids for Singlet Fission: Cibalackrot". United States. doi:10.1063/1.5121863. https://www.osti.gov/servlets/purl/1572370.
@article{osti_1572370,
title = {Structure and Photophysics of Indigoids for Singlet Fission: Cibalackrot},
author = {Ryerson, Joseph L. and Zaykov, Alexandr and Aguilar Suarez, Luis E. and Havenith, Remco W. A. and Stepp, Brian R. and Dron, Paul I. and Kaleta, Jirí and Akdag, Akin and Teat, Simon J. and Magnera, Thomas F. and Miller, John R. and Havlas, Zdenek and Broer, Ria and Faraji, Shirin and Michl, Josef and Johnson, Justin C.},
abstractNote = {Here, 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. Here, 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.},
doi = {10.1063/1.5121863},
journal = {Journal of Chemical Physics},
number = 18,
volume = 151,
place = {United States},
year = {2019},
month = {11}
}

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