Phenyl-Substituted Cibalackrot Derivatives: Synthesis, Structure, and Solution Photophysics
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- Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences, Flemingovo nám. 2, 16610 Prague, Czech Republic
- J. Heyrovsky Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejškova 3, 182 23 Prague 8, Czech Republic
- Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences, Flemingovo nám. 2, 16610 Prague, Czech Republic, University of Chemistry and Technology, Technicka 5, 16000 Prague 6, Czech Republic
- Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720-1460, United States
- Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences, Flemingovo nám. 2, 16610 Prague, Czech Republic, Department of Chemistry, University of Colorado, Boulder, Colorado 80309-0215, United States
Three symmetrically and three unsymmetrically substituted cibalackrot (7,14-diphenyldiindolo[3,2,1-de:3',2',1'-ij][1,5]naphthyridine-6,13- dione, 1) dyes carrying two derivatized phenyl rings have been synthesized as candidates for molecular electronics and especially for singlet fission, a process of interest for solar energy conversion. Solution measurements provided singlet and triplet excitation energies and fluorescence yields and lifetimes; conformational properties were analyzed computationally. The molecular properties are close to ideal for singlet fission. However, crystal structures, obtained by single-crystal X-ray diffraction (XRD), are rather similar to those of the polymorphs of solid 1, in which the formation of a charge-separated state followed by intersystem crossing, complemented with excimer formation, outcompetes singlet fission. Results of calculations by the approximate SIMPLE method suggest which ones among the solid derivatives are the best candidates for singlet fission, but it appears difficult to change the crystal packing in a desirable direction. We also describe the preparation of three specifically deuteriated versions of 1, expected to help sort out the mechanism of fast intersystem crossing in its charge-separated state.
- Research Organization:
- Univ. of Colorado, Boulder, CO (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
- Grant/Contract Number:
- SC0007004; AC02-05CH11231
- OSTI ID:
- 1974836
- Alternate ID(s):
- OSTI ID: 1976116
- Journal Information:
- Journal of Organic Chemistry, Journal Name: Journal of Organic Chemistry Vol. 88 Journal Issue: 11; ISSN 0022-3263
- Publisher:
- American Chemical SocietyCopyright Statement
- Country of Publication:
- United States
- Language:
- English
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