Highly luminescent crystals of a novel linear π-conjugated thiophene–phenylene co-oligomer with a benzothiadiazole fragment

Postnikov, V. A.; Сорокина, Н. И.; Kulishov, A. A.; Lyasnikova, M. S.; Гребенев, В. В.; Волошин, А. Э.; Borshchev, Oleg V.; Skorotetcky, Maxim S.; Сурин, Н. М.; Svidchenko, Evgeniya A.; Ponomarenko, Sergei A.

doi:10.1107/s2052520619012484

Cited by 8 publications

(12 citation statements)

References 34 publications

(34 reference statements)

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“…One of the approaches to increase solubility of the oligomer in order to improve its crystal growth characteristics is to add branched terminal substituents into the molecular structure. However, this approach will naturally lead to a change in the crystal structure, which will be more friable, and, accordingly, to a greater or lesser extent, will affect the electrical and optical properties of the crystals [16][17][18][19][20]. Without changing the chemical structure, it is possible to significantly improve the solubility of the oligomer due to a substantial increase in the solution temperature.…”

Section: Introductionmentioning

confidence: 99%

Large Area Free-Standing Single Crystalline Films of p-Quinquephenyl: Growth, Structure and Photoluminescence Properties

et al. 2020

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Studies of the growth of large-area free-standing single-crystalline films of p-quinquephenyl are presented. High-quality crystals were grown by slow cooling of a hot chlorobenzene solution. Worse quality large-area free-standing single crystals of p-quinquephenyl were also grown by using physical vapor transport and used for comparison. The crystal structure of p-quinquephenyl at 293 K and 85 K was refined by single-crystal X-ray diffraction. The optical absorption and photoluminescence spectra of solutions and crystalline films were obtained and analyzed; a positive solvatochromic effect was detected.

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Section: Introductionmentioning

confidence: 99%

Large Area Free-Standing Single Crystalline Films of p-Quinquephenyl: Growth, Structure and Photoluminescence Properties

et al. 2020

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“…These monolayers consist of two subsystems of the densest molecular rows slightly displaced relative to each other along the c axis, oriented in the direction of the a axis (in Figure c, the densest rows of molecules in the projection onto the drawing plane are highlighted in gray and yellow). In the projection onto the (100) plane, the densest rows of molecules form a “brickwork” structure (Figure c), which, as a rule, is a characteristic feature for linear conjugated molecules with 1D anisotropic crystal growth. , In such cases, the crystal growth rate is maximal in the direction close to the direction of the densest rows, within which the strongest interactions take place between the nearest molecules (Figure S5a).…”

Section: Resultsmentioning

confidence: 94%

“…Crystal growth was carried out by the method of isothermal evaporation of the solvent at room temperature …”

Section: Methodsmentioning

confidence: 99%

“…Good candidates for this task are rather short linear conjugated molecules with a sufficiently high solubility in standard organic solvents as well as stable over a wide operating temperature range. It should be noted that crystallization of the molecules with a central BTD fragment is still scarcely studied in the literature, , and there are no data on the growth of bulk single crystals at a scale of ∼1 cm.…”

Section: Introductionmentioning

confidence: 99%

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

Postnikov,

Sorokina,

Kulishov

et al. 2024

ACS Omega

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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. P1̅ , Z = 4), and for (TMS-P) 2 -BTD crystals, the structure has been solved for the first time (sp. gr. P2 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.

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“…Unfortunately, very few details of crystal growth techniques are described in these works. Our recent studies have shown that an oligomer containing a central BTD fragment, six conjugated thiophene and phenylene groups, and terminal trimethylsilyl substituents crystallizes well from solutions in the form of needle crystals of centimetre scale and is characterized by a high quantum yield of fluorescence in solutions and in the crystalline state (Postnikov et al, 2019b). In terms of optical properties, oligomers consisting of phenylene and oxazole groups are among the most efficient luminophores (Yan et al, 2013;Skorotetcky et al, 2017).…”

Section: Introductionmentioning

confidence: 99%

A new linear phenyloxazole–benzothiadiazole luminophore: crystal growth, structure and fluorescence properties

Postnikov

Сорокина

Kulishov

et al. 2022

Acta Crystallogr Sect B

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A new linear luminophore consisting of five conjugated units of oxazole, phenylene and a central benzothiadiazole fragment, 4,7-bis[4-(1,3-oxazol-5-yl)phenyl]-2,1,3-benzothiadiazole, has been synthesized and characterized. Needle-like single-crystal samples up to 10 mm in length were obtained by physical vapor transport. The crystal structure was determined at 95 K and 293 K using single-crystal X-ray diffraction. With decreasing temperature, the space group P21/n does not change, but the unit-cell volume of the crystal decreases. The presence of intra- and intermolecular hydrogen bonds was established. Melting parameters (T m = 305.5°C, ΔH m = 52.2 kJ mol−1) and the presence of a liquid-crystalline mesophase (T LC = 336.3°C, ΔH LC = 1.4 kJ mol−1) were determined by differential scanning calorimetry and in situ thermal polarization optical microscopy studies. The presence of linear chains of hydrogen bonds ensures high stability of the crystal structure in a wide temperature range. The luminophore is characterized by a large Stokes shift (5120–5670 cm−1) and a high quantum yield of fluorescence, reaching 96% in solutions (λmax = 517 nm) and 27% in thin crystalline films (λmax = 529 nm). The calculated absorption and emission spectra are in good agreement with the experimental data. Because of the excellent optical properties and high thermal stability, the new linear luminophore has great potential for application in organic photonics and optoelectronic devices.

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Highly luminescent crystals of a novel linear π-conjugated thiophene–phenylene co-oligomer with a benzothiadiazole fragment

Cited by 8 publications

References 34 publications

Large Area Free-Standing Single Crystalline Films of p-Quinquephenyl: Growth, Structure and Photoluminescence Properties

Large Area Free-Standing Single Crystalline Films of p-Quinquephenyl: Growth, Structure and Photoluminescence Properties

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

A new linear phenyloxazole–benzothiadiazole luminophore: crystal growth, structure and fluorescence properties

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