Intramolecular H-type dimer and excimer formation in dibenzoylmethanatoboron difluoride dyads connected via diphenylsiloxane linkers

Belova, Anastasia S.; Kononevich, Yuriy N.; Ionov, D. S.; Sazhnikov, V. A.; Volodin, Alexander D.; Korlyukov, Аlexander А.; Дороватовский, Павел В.; Алфимов, М. В.; Музафаров, А. М.

doi:10.1016/j.dyepig.2022.110852

Cited by 5 publications

(21 citation statements)

References 91 publications

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“…The contributions of fast kinetics increase with increasing solvent polarity. The obtained kinetics resemble the decays obtained for the DBMBF 2 connected with diphenylsiloxane linkers described previously by us [ 62 ], although the contribution of fast kinetics at 540 nm is much higher. The same model discussed for the dyads may be proposed for polymer 3 b , but the results obtained for polymer 3 a and the third exponential term observed at 540 nm for 3 b in dichloromethane indicate that the observed fluorescence kinetics are more complex in nature.…”

Section: Resultssupporting

confidence: 84%

“…In the case of polymers 3 a,b , the fluorescence spectra contain additional wide unstructured low-energy bands with maxima at about 550 nm. Such behavior has been observed earlier in similar siloxane-containing systems [ 61 , 62 , 63 ] and is related to the excimer-like fluorescence. Polymer 3 a , which contained more frequently grafted DBMBF 2 fragments (each 25th unit), tended to form many more excimers than polymer 3 b with a sparse distribution of DBMBF 2 fragments (each 200th unit), as clearly shown by the comparison of I ex /I m ratio ( Table 2 ).…”

Section: Resultssupporting

confidence: 80%

“…It is noteworthy that in the case of nonpolar solvents, such as cyclohexane, the intensity of the 0–0 transition drops significantly compared with the 0–1 transition. This behavior indicates the existence of intramolecular H-dimers in the ground state and has been described in detail in our previous work [ 62 ]. As shown in Figure 22 , in the case of polymer 3 a with a higher concentration of grafted DBMBF 2 fragments, the content of H-dimers is much higher than in the case of polymer 3 b .…”

Section: Resultssupporting

confidence: 75%

“…Continuing our study of the behavior of DBMBF 2 derivatives connected through flexible siloxane linker [ 62 , 63 ], in the present work the method for the preparation and properties of polydimethylsiloxanes with grafted dibenzoylmethanatoboron difluoride has been described for the first time. The structures of the prepared polymers were confirmed using NMR, IR spectroscopy and gel permeation chromatography (GPC) methods.…”

Section: Introductionmentioning

confidence: 99%

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Polydimethylsiloxanes with Grafted Dibenzoylmethanatoboron Difluoride: Synthesis and Properties

et al. 2022

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A method for the preparation of polydimethylsiloxanes with grafted methoxy-substituted dibenzoylmethanatoboron difluoride has been described. The structures of prepared polymers were confirmed using NMR, IR spectroscopy and gel permeation chromatography methods. Their thermal properties were investigated using thermal gravimetric analysis, differential scanning calorimetry and thermomechanical analysis. The prepared polymers had good thermal (Td5% up to 393 °C) and thermo-oxidative (Td5% = 413 °C) stability. The polymers started to transit in a viscous flow state at about 40 °C (for 3 a) and at about 20 °C (for 3 b). The viscoelastic characteristics of prepared polymers were determined in the sinusoidal oscillating vibrations mode. It was shown that the studied polymers at low frequencies at room temperature are viscoelastic fluids (G′ < G″). Increasing the frequency led to inversion (crossover) of dependences G′ and G″, which indicated the transition of polymers from viscous to elastomeric behavior characteristics, and the beginning of the formation of a physical network. Optical properties were studied using electron absorption, steady-state and time-resolved fluorescence spectroscopy. It was shown that intramolecular H-dimers exist in the ground state. The polymers studied had a bright fluorescence in the solution and in the solid state, consisting of bands of monomer and excimer emission. Thermally-activated delayed fluorescence was observed in the solution and the solid state. The prepared polymers possess intriguing properties that make them useful as optical materials, sensors or imaging agents.

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Section: Resultssupporting

confidence: 84%

Section: Resultssupporting

confidence: 80%

Section: Resultssupporting

confidence: 75%

Section: Introductionmentioning

confidence: 99%

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Polydimethylsiloxanes with Grafted Dibenzoylmethanatoboron Difluoride: Synthesis and Properties

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“…Ph 2 Si[OSi(CH 3 ) 2 H] 2 (0.10 g, 0.30 mmol, 1 equiv) was prepared according to the procedure reported in ref using modifier 3 (0.16 g, 0.69 mmol, 2.3 equiv), toluene (2.7 mL), and Karstedt’s catalyst (2 μL; 0.07 mol %) to give the product as a viscous transparent brownish liquid ( 1 H, 11 B, 13 C, and 29 Si NMR, IR, and HRMS spectra) in 92% yield (0.22 g, 0.28 mmol).…”

Section: Experimental Sectionmentioning

confidence: 99%

Synthesis of Siloxane Derivatives of Phenylboronic Acids of Different Structures

et al. 2023

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The synthesis of a storage-stable organosilicon modifier with a dioxaborolane-protecting group is described. Its high reactivity and selective anti-Markovnikov addition in hydrosilylation reactions to afford siloxanes of various structures are shown. The possibility of deprotection of both the initial modifier and its siloxane derivatives under mild conditions using water in yields up to 96% is demonstrated. The existence of an equilibrium between the organosilicon derivatives of phenylboronic acids and their cyclic six-membered boroxines was confirmed by 1 H NMR spectroscopy and X-ray diffraction analysis data. The use of siloxane derivatives of phenylboronic acids in Suzuki−Miyaura and Chan−Lam cross-coupling reactions was studied. All synthesized compounds were characterized by NMR ( 1 H, 11 B, 13 C, and 29 Si), IR spectroscopy, and high-resolution mass spectrometry.

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Tetrachromophoric Derivatives of Dibenzoylmethanatoboron Difluoride Based on Stereoregular Cyclotetrasiloxanes: Synthesis and Properties

et al. 2023

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A series of new tetrachromophoric systems based on stereoregular tetracyclosiloxanes and dibenzoylmethanatoboron difluoride derivatives have been synthesized and characterized by a complex of physicochemical methods. The photophysical properties of the synthesized compounds are studied by electronic absorption, steady-state, and time-resolved fluorescence spectroscopy. In the synthesized compounds, four dibenzoylmethanatoboron difluoride (DBMBF2)-based fluorophores are in an all-cis arrangement with respect to a cyclotetrasiloxane scaffold. DFT calculations predict that they can form H-type dimers, trimers, or tetramers with an antiparallel orientation of their ground-state dipole moments. Under UV excitation, solutions of these compounds in polar and nonpolar solvents exhibit complex fluorescence consisting of monomer- and excimer-like emissions with different lifetimes. Global fitting analysis reveals the presence of at least four kinetically distinguishable species in the excited state. The studied compounds in solutions have CIE chromaticity coordinates very close to the white color point and are promising objects for the development of next-generation single-emission materials for white illumination.

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Intramolecular H-type dimer and excimer formation in dibenzoylmethanatoboron difluoride dyads connected via diphenylsiloxane linkers

Cited by 5 publications

References 91 publications

Polydimethylsiloxanes with Grafted Dibenzoylmethanatoboron Difluoride: Synthesis and Properties

Polydimethylsiloxanes with Grafted Dibenzoylmethanatoboron Difluoride: Synthesis and Properties

Synthesis of Siloxane Derivatives of Phenylboronic Acids of Different Structures

Tetrachromophoric Derivatives of Dibenzoylmethanatoboron Difluoride Based on Stereoregular Cyclotetrasiloxanes: Synthesis and Properties

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