Crystals of Diphenyl-Benzothiadiazole and Its Derivative with Terminal Trimethylsilyl Substituents: Growth from Solutions, Structure, and Fluorescence Properties.

Autor:	Postnikov VA; Kurchatov Complex of Crystallography and Photonics of the National Research Centre 'Kurchatov Institute', Leninsky Prosp. 59, Moscow, 119333, Russian Federation.; Enikolopov Institute of Synthetic Polymer Materials of Russian Academy of Sciences, Profsoyuznaya St. 70, Moscow 117393, Russian Federation., Sorokina NI; Kurchatov Complex of Crystallography and Photonics of the National Research Centre 'Kurchatov Institute', Leninsky Prosp. 59, Moscow, 119333, Russian Federation., Kulishov AA; Kurchatov Complex of Crystallography and Photonics of the National Research Centre 'Kurchatov Institute', Leninsky Prosp. 59, Moscow, 119333, Russian Federation.; Enikolopov Institute of Synthetic Polymer Materials of Russian Academy of Sciences, Profsoyuznaya St. 70, Moscow 117393, Russian Federation., Yurasik GA; Kurchatov Complex of Crystallography and Photonics of the National Research Centre 'Kurchatov Institute', Leninsky Prosp. 59, Moscow, 119333, Russian Federation.; Enikolopov Institute of Synthetic Polymer Materials of Russian Academy of Sciences, Profsoyuznaya St. 70, Moscow 117393, Russian Federation., Sorokin TA; Kurchatov Complex of Crystallography and Photonics of the National Research Centre 'Kurchatov Institute', Leninsky Prosp. 59, Moscow, 119333, Russian Federation.; Enikolopov Institute of Synthetic Polymer Materials of Russian Academy of Sciences, Profsoyuznaya St. 70, Moscow 117393, Russian Federation., Lyasnikova MS; Kurchatov Complex of Crystallography and Photonics of the National Research Centre 'Kurchatov Institute', Leninsky Prosp. 59, Moscow, 119333, Russian Federation., Borshchev OV; Enikolopov Institute of Synthetic Polymer Materials of Russian Academy of Sciences, Profsoyuznaya St. 70, Moscow 117393, Russian Federation., Skorotetcky MS; Enikolopov Institute of Synthetic Polymer Materials of Russian Academy of Sciences, Profsoyuznaya St. 70, Moscow 117393, Russian Federation., Pisarev SA; Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory 1/3, Moscow 119991, Russian Federation.; Enikolopov Institute of Synthetic Polymer Materials of Russian Academy of Sciences, Profsoyuznaya St. 70, Moscow 117393, Russian Federation., Svidchenko EA; Enikolopov Institute of Synthetic Polymer Materials of Russian Academy of Sciences, Profsoyuznaya St. 70, Moscow 117393, Russian Federation., Surin NM; Enikolopov Institute of Synthetic Polymer Materials of Russian Academy of Sciences, Profsoyuznaya St. 70, Moscow 117393, Russian Federation., Ponomarenko SA; Enikolopov Institute of Synthetic Polymer Materials of Russian Academy of Sciences, Profsoyuznaya St. 70, Moscow 117393, Russian Federation.
Jazyk:	angličtina
Zdroj:	ACS omega [ACS Omega] 2024 Mar 21; Vol. 9 (13), pp. 14932-14946. Date of Electronic Publication: 2024 Mar 21 (Print Publication: 2024).
DOI:	10.1021/acsomega.3c08543
Abstrakt:	Linear conjugated molecules consisting of benzothiadiazole (BTD) and phenyl rings are highly efficient organic luminophores. Crystals based on these compounds have great potential for use as light-emitting elements, in particular, scintillation detectors. This paper compares the peculiarities of growth, structure, and fluorescent properties of crystals based on 4,7-diphenyl-2,1,3-benzothiadiazole ( P 2 -BTD ) and its organosilicon derivative 4,7-bis(4-(trimethylsilyl)phenyl) BTD ( (TMS-P) 2 -BTD ). The conditions for the formation of centimeter-scale single crystals were found for the former, while it was possible to prepare also bulky faceted individual crystals for the latter. The structures of P 2 -BTD and (TMS-P) 2 -BTD crystals at 85 and 293 K were investigated by single-crystal X-ray diffraction. The crystal structure of P 2 -BTD has been refined (sp. gr. P 1̅, Z = 4), and for (TMS-P) 2 -BTD crystals, the structure has been solved for the first time (sp. gr. P 2 1 / c , Z = 32). Experimental and theoretical investigations of the absorption-fluorescent properties of solutions and crystals of the molecules have been carried out. The luminophores are characterized by a large Stokes shift for both solutions and crystals with a high fluorescence quantum yield of 75-98% for solutions and 50-85% for the crystals. A solvatochromic effect was observed for solutions of both luminophores: an increase in the values of the fluorescence quantum yield and the excited state lifetime were established with increasing the solvent polarity. Fluorescence properties of solutions and crystals have been analyzed using the data on crystal structure and conformation structure of the molecules as well as density functional theory calculations of their electronic structure. The results have shown that the crystal packing of P 2 -BTD molecules exhibits uniformity in conformational states, while (TMS-P) 2 -BTD molecules display a variety of conformational structures in the crystals. This unique combination of features makes them a remarkable example among the other molecular systems for identifying the relationship between the structure and absorption-fluorescence properties through comparative analysis. Competing Interests: The authors declare no competing financial interest. (© 2024 The Authors. Published by American Chemical Society.)
Databáze:	MEDLINE
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