Crystals of 4,7-bis(2,5-dimethyl-[1,1'-biphenyl]-4-yl)benzothiadiazole and Its Derivative with Terminal n-Hexyl Substitutes: Growth, Structure, Thermal and Absorption-Fluorescent Properties

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Abstract

This study presents an investigation into the crystallization and absorptive-fluorescent properties of linear conjugated molecules derived from 2,1,3-benzothiadiazole, specifically 4,7-bis(2,5-dimethyl-[1,1'-biphenyl]-4-yl)benzothiadiazole (Ph-Xy-BTD) and 4,7-bis(4'-hexyl-2,5-dimethyl-[1,1'-biphenyl]-4-yl)benzothiadiazole (Hex-Ph-Xy-BTD). The synthesis of a new derivative of Hex-Ph-Xy-BTD is described. It was found that the presence of terminal n-hexyl substituents in Hex-Ph-Xy-BTD leads to a lower melting point, increased solubility and has a positive effect on crystallization compared to Ph-Xy-BTD. Single crystals of Hex-Ph-Xy-BTD were grown from hexane solution, and their structure was elucidated using single-crystal X-ray diffraction, confirming a monoclinic system (space group P21/c, Z = 4). Absorption and fluorescence spectra were obtained and analyzed for solutions in tetrahydrofuran as well as for the crystals of Ph-Xy-BTD and Hex-Ph-Xy-BTD, alongside investigations of quantum yield and fluorescence lifetime.

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About the authors

V. A. Postnikov

Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics of NRC “Kurchatov Institute”

Author for correspondence.
Email: postva@yandex.ru
Russian Federation, Moscow

N. I. Sorokina

Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics of NRC “Kurchatov Institute”

Email: postva@yandex.ru
Russian Federation, Moscow

G. A. Yurasik

Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics of NRC “Kurchatov Institute”

Email: postva@yandex.ru
Russian Federation, Moscow

Т. А. Сорокин

Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics of NRC “Kurchatov Institute”

Email: postva@yandex.ru
Russian Federation, Moscow

A. A. Kylishov

Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics of NRC “Kurchatov Institute”

Email: postva@yandex.ru
Russian Federation, Moscow

M. S. Lyasnikova

Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics of NRC “Kurchatov Institute”

Email: postva@yandex.ru
Russian Federation, Moscow

V. V. Popova

Enikolopov Institute of Synthetic Polymer Materials of Russian Academy of Sciences

Email: postva@yandex.ru
Russian Federation, Moscow

E. A. Svidchenko

Enikolopov Institute of Synthetic Polymer Materials of Russian Academy of Sciences

Email: postva@yandex.ru
Russian Federation, Moscow

N. M. Surin

Enikolopov Institute of Synthetic Polymer Materials of Russian Academy of Sciences

Email: postva@yandex.ru
Russian Federation, Moscow

O. V. Borshchev

Enikolopov Institute of Synthetic Polymer Materials of Russian Academy of Sciences

Email: borshchev@ispm.ru
Russian Federation, Moscow

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Supplementary files

Supplementary Files
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2. Rice. 1. Synthesis scheme for Hex-Ph-Xy-BTD.

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3. Fig. 2. DSC curves for Hex-Ph-Xy-BTD (1) and Ph-Xy-BTD (2).

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4. Fig. 3. Ph-Xy-BTD crystals: on graph paper (a) and fluorescent image of a crystalline aggregate (b).

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5. Fig. 4. Hex-Ph-Xy-BTD crystals: under UV illumination (a), confocal image of a faceted crystal (b) and its images in fluorescence mode (c) and in differential interference contrast mode (d).

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6. Fig. 5. Conformation of the Hex-Ph-Xy-BTD molecule in the ORTEP representation with indication of torsion angles between conjugated groups (thermal ellipsoids with a probability level of 50%).

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7. Fig. 6. Structure of Hex-Ph-Xy-BTD crystals: projection of the structure onto the (010) plane (a), projection of molecules in adjacent closest rows onto the (001) plane with the shortest H H and C-H π contacts indicated (b), diagram of the shortest contacts between nearest neighbors (c).

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8. Fig. 7. Element of a crystalline monolayer in the orientation of the (100) plane (a) and software reconstruction of the Hex-Ph-Xy-BTD crystal habit (b).

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9. Fig. 8. X-ray powder diffraction patterns for Ph-Xy-BTD (1) and Hex-Ph-Xy-BTD (2).

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10. Fig. 9. Normalized absorption and fluorescence spectra of Ph-Xy-BTD (a) and Hex-Ph-Xy-BTD (b) in THF solution and in a thin polycrystalline film (without reabsorption). Selection of the absorption band of fluorescence centers (band I) in a thin polycrystalline film. Excitation was carried out in the long-wave absorption maximum.

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11. Fig. 10. Normalized absorption and fluorescence spectra of Ph-Xy-BTD (a) and Hex-Ph-Xy-BTD (b) of thin (1) and bulk (2) crystals. Excitation was carried out at the long-wave absorption maximum.

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