The Charge Transfer Complex Formed between the Components of Photopolymer Material as an Internal Sensitizer of Spectral Sensitivity
Full article
| Общее |
Language:
Английский,
Genre:
Full article,
Status:
Published,
Source type:
Original
|
| Journal |
ChemistrySelect
, E-ISSN: 2365-6549
|
| Output data |
Year: 2020,
Volume: 5,
Number: 38,
Pages: 11939-11947
Pages count
: 9
DOI:
10.1002/slct.202002163
|
| Tags |
charge transfer; density functional calculations.; Photopolymer material; sulfonium salt; thermodynamics |
| Authors |
Derevyanko Dmitry I.
1
,
Shelkovnikov Vladimir V.
1,2
,
Kovalskii Victor Y.
3
,
Zilberberg Igor L.
3,4
,
Aliev Sergei I.
1,2
,
Orlova Natalya A.
1
,
Ugozhaev Vladimir D.
5
|
| Affiliations |
| 1 |
Laboratory of Organic Photosensitive Materials, N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry of Siberian Branch of Russian Academy of Sciences, 9 Lavrentiev Ave.
|
| 2 |
Novosibirsk State Technical University, 20 Prospekt K. Marksa, Novosibirsk 630073 (Russia)
|
| 3 |
Laboratory of Quantum Chemistry, Boreskov Institute of Catalysis SB RAS, 5 Lavrentiev Ave., Novosibirsk 630090 (Russia)
|
| 4 |
Novosibirsk State University, 1, Pirogova str., Novosibirsk 630090 (Russia)
|
| 5 |
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 (Russia)
|
|
Funding (2)
|
1
|
Russian Foundation for Basic Research
|
18-33-00932
|
|
2
|
Russian Science Foundation
|
18-73-00226 (АААА-А19-119090990063-7)
|
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