Phenyl-Substituted Cibalackrot Derivatives: Synthesis, Structure, and Solution Photophysics

0573362 - ÚOCHB 2024 RIV US eng J - Journal Article
Kaleta, Jiří - Dudič, Miroslav - Ludvíková, Lucie - Liška, Alan - Zaykov, Alexandr - Rončević, Igor - Mašát, Milan - Bednárová, Lucie - Dron, Paul Ionut - Teat, S. J. - Michl, Josef
Phenyl-Substituted Cibalackrot Derivatives: Synthesis, Structure, and Solution Photophysics.
Journal of Organic Chemistry. Roč. 88, č. 11 (2023), s. 6573-6587. ISSN 0022-3263. E-ISSN 1520-6904
R&D Projects: GA ČR(CZ) GA19-22806S
Research Infrastructure: e-INFRA CZ - 90140
Institutional support: RVO:61388963 ; RVO:61388955
Keywords : singlet exciton fission * photolysis * efficiency
OECD category: Organic chemistry; Physical chemistry (UFCH-W)
Impact factor: 3.6, year: 2022
Method of publishing: Open access
https://doi.org/10.1021/acs.joc.2c02706

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.
Permanent Link: https://hdl.handle.net/11104/0343825


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