The Charge Transfer Complex Formed between the Components of Photopolymer Material as an Internal Sensitizer of Spectral Sensitivity

The Charge Transfer Complex Formed between the Components of Photopolymer Material as an Internal Sensitizer of Spectral Sensitivity Научная публикация

Журнал

ChemistrySelect
ISSN: 2365-6549

Вых. Данные

Год: 2020, Том: 5, Номер: 38, Страницы: 11939-11947 Страниц : 9 DOI: 10.1002/slct.202002163

Ключевые слова

charge transfer; density functional calculations.; Photopolymer material; sulfonium salt; thermodynamics

Авторы

Derevyanko D.I. ¹ , Shelkovnikov V.V. ^1,2 , Kovalskii V.Y. ³ , Zilberberg I.L. ^3,4 , Aliev S.I. ^1,2 , Orlova N.A. ¹ , Ugozhaev V.D. ⁵

Организации

1	(Scopus) Laboratory of Organic Photosensitive Materials N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry of Siberian Branch of Russian Academy of Sciences, 9 Lavrentiev Ave., Russian Federation
2	(Scopus) Novosibirsk State Technical University 20 Prospekt K. Marksa, Novosibirsk, 630073, Russian Federation
3	(Scopus) Laboratory of Quantum Chemistry Boreskov Institute of Catalysis SB RAS, 5 Lavrentiev Ave., Novosibirsk, 630090, Russian Federation
4	(Scopus) Novosibirsk State University 1, Pirogova str., Novosibirsk, 630090, Russian Federation
5	(Scopus) Laboratory of physics of lasers Institute of Automation and Electrometry of the Siberian Branch of the Russian Academy of Sciences, 1 Academician Koptyug ave., Novosibirsk, 630090, Russian Federation

A photosensitive charge transfer complex (CTC) is formed between the components of the photopolymer material: the tetra–acrylate monomer synthesized from dihydroxydiphenyl sulfide (TADDS) and a photoinitiator, a cationic sulfonium salt synthesized from diethylthioxanthen-9-one (SSDETX). It allows one to perform laser recording of the microstructures in the hybrid photopolymer material using absorption of CTC at λ=473 nm. The 1 : 1 molecular composition of CTC was confirmed by applying the Job's method of continuous variation to determine the stoichiometry. The association constant (KAS(278°K)=17 L mol−1) was calculated using the modified Benesi-Hildebrand equation. The thermodynamic parameters, such as enthalpy (ΔH=−15.63 kJ mol), entropy (ΔS°=−32.6 J mol−1 K−1), and the Gibbs free energy (ΔG=−6.63 kJ mol−1) were calculated using the Van't Hoff equation. These results indicate that CTC formation is an exothermic reaction. The experimental findings were supplemented by density functional theory (DFT) study of CTCs at the UB3LYP/6-311G level as implemented in the Gaussian 09 software package. Charge transfer excitations were simulated by means of the time-dependent density functional theory (TDDFT) approach. The DFT-calculated spectra agree with the experimental data of spectral and photochemical properties of the [SSDETX-TADDS] CTC. © 2020 Wiley-VCH GmbH

Derevyanko D.I. , Shelkovnikov V.V. , Kovalskii V.Y. , Zilberberg I.L. , Aliev S.I. , Orlova N.A. , Ugozhaev V.D.
The Charge Transfer Complex Formed between the Components of Photopolymer Material as an Internal Sensitizer of Spectral Sensitivity
ChemistrySelect. 2020. V.5. N38. P.11939-11947. DOI: 10.1002/slct.202002163 WOS Scopus

Опубликована online:	13 окт. 2020 г.
Опубликована в печати:	15 окт. 2020 г.

Web of science	WOS:000577627200033
Scopus	2-s2.0-85092601399
OpenAlex	W3093841058