Molecular Environment Effects That Modulate the Photophysical Properties of Novel 1,3-Phosphinoamines Based on 2,1,3-Benzothiadiazole

Molecular Environment Effects That Modulate the Photophysical Properties of Novel 1,3-Phosphinoamines Based on 2,1,3-Benzothiadiazole Full article

Journal

Molecules
ISSN: 1420-3049

Output data

Year: 2022, Volume: 27, Number: 12, Article number : 3857, Pages count : 13 DOI: 10.3390/molecules27123857

Authors

Khisamov Radmir M. ¹ , Ryadun Alexey A. ¹ , Konchenko Sergey N. ^1,2 , Sukhikh Taisiya S. ^1,2

Affiliations

1	Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences
2	Department of Natural Sciences, National Research University—Novosibirsk State University

We report synthesis, crystal structure, and photophysical properties of novel 1,3- phosphinoamines based on 4-amino-2,1,3-benzothiadiazole (NH2-btd): Ph2PCH(Ph)NH-btd (1) and Ph2P(E)CH(Ph)NH-btd, (E = O (2 and 2thf), S (3), Se (4)). Chalcogenides 2–4 exhibit bright emissions with a major band at 519–536 nm and a minor band at 840 nm. According to TD-DFT calculations, the first band is attributed to fluorescence, while the second band corresponds to phosphorescence. In the solid state, room temperature quantum yield reaches 93% in the case of the sulphide. The compounds under study feature effects of the molecular environment on the luminescent properties, which manifest themselves in fluorosolvatochromism as well as in a luminescent response to changes in crystal packing and in contributions to aggregation effects. Specifically, transformation of solid 2thf to solvate-free 2 either by aging or by grinding causes crystal packing changes, and, as a result, a hypsochromic shift of the emission band. Polystyrene films doped with 2 reveal a bathochromic shift upon increasing the mass fraction from 0.2 to 3.3%, which is caused by molecular aggregation effects.

Khisamov R.M. , Ryadun A.A. , Konchenko S.N. , Sukhikh T.S.
Molecular Environment Effects That Modulate the Photophysical Properties of Novel 1,3-Phosphinoamines Based on 2,1,3-Benzothiadiazole
Molecules. 2022. V.27. N12. 3857 :1-13. DOI: 10.3390/molecules27123857 WOS Scopus РИНЦ OpenAlex

Web of science:	WOS:000816129600001
Scopus:	2-s2.0-85132586787
Elibrary:	49151270
OpenAlex:	W4283074177

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