Electron‐Withdrawing Substituted Quinazoline Push‐Pull Chromophores: Synthesis, Electrochemical, Photophysical and Second‐Order Nonlinear Optical Properties

Moshkina, Tatiana N.; Poul, Pascal Le; Barsella, Alberto; Pytela, Oldřich; Bureš, Filip; Guen, Françoise Robin‐le; Achelle, Sylvain; Носова, Э. В.; Lipunova, G. N.; Charushin, Valery N.

doi:10.1002/ejoc.202000870

Cited by 21 publications

(17 citation statements)

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“…Incorporation of 4-cyanoquinazoline or quinazolin-4(3 H )-one cores allows to reinforce the electron-withdrawing properties. We described synthesis and photophysical properties of 4-cyano-2-thienylquinazoline derivatives [ 31 ], and we confirmed the strong electron withdrawing nature of 4-cyanoquinazoline core. On the other hand, quinazolin-4(3 H )-one bearing 5-(4-diethylaminophenyl)thiophen-2-yl substituent at the position 2 possesses strong photoluminescence in the solution [ 32 ].…”

Section: Introductionmentioning

confidence: 76%

“…Synthetic approach to 4-cyano-2-thienylquinazolines 7 was developed by our research group earlier [ 31 , 32 ]. It includes nucleophilic substitution of chorine atom at position 4 of quinazoline core by the CN group in DMF under heating and subsequent Suzuki-Miyaura cross-coupling with arylboronic acid.…”

Section: Resultsmentioning

confidence: 99%

“…The introduction of the CN-group into position 4 of quinazoline core leads to red/orange-colored compounds with poor emission under UV-light ( Figure 6 ). The emission spectra of cyano-derivatives 7a–c [ 31 ], 8a,b and 9 display two maxima with low intensity ( Table 2 ). The dual emission can be ascribed to stabilization of two lowest exited states (ICT and TICT) caused by dimer formation through the CN group [ 32 ].…”

Section: Resultsmentioning

confidence: 99%

“…The reaction mixture was cooled. After cooling, the target product was filtered off and washed with water and hexane [ 29 , 30 , 31 ].…”

Section: Experimental Methodsmentioning

confidence: 99%

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Push-Pull Structures Based on 2-Aryl/thienyl Substituted Quinazolin-4(3H)-ones and 4-Cyanoquinazolines

et al. 2022

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Design and synthesis of 2-(aryl/thiophen-2-yl)quinazolin-4(3H)-ones and 4-cyano-2-arylquinazolines with Et2N-, Ph2N- or carbazol-9-yl- electron donating fragment are described. The key photophysical properties of these compounds have been studied by UV/Vis absorption and fluorescence spectroscopy in solvents of different polarity (toluene and MeCN). 2-(Aryl/thiophen-2-yl)quinazolin-4(3H)-ones show fluorescence in blue-green region in toluene solution with quantum yields up to 89% in the case of 2-(4’-N,N-diphenylamino[1,1’-biphenyl]-4-yl)-quinazolin-4(3H)-one. Moreover, triphenylamino derivative based on quinazolin-4(3H)-one with para-phenylene linker displays the highest quantum yield of 40% in powder. The fluorescence QY of Et2N and Ph2N derivatives decrease when going from toluene to MeCN solution, whereas carbazol-9-yl counterparts demonstrate strengthening of intensity that emphasizes the strong influence of donor fragment nature on photophysical properties. 4-Cyanoquinazolines are less emissive in both solvents, as well as, in solid state. The introduction of cyano group into position 4 leads to orange/red colored powder and dual emission bands. Some molecules demonstrate the increase in emission intensity upon addition of water to MeCN solution. According to frontier molecular orbitals (HOMO, LUMO) calculations, the energy gap of 4-cyanoquinazoline decreases by more than 1 eV compared to quinazolin-4-one, that is consistent with experimental data.

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Section: Introductionmentioning

confidence: 76%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

“…The reaction mixture was cooled. After cooling, the target product was filtered off and washed with water and hexane [ 29 , 30 , 31 ].…”

Section: Experimental Methodsmentioning

confidence: 99%

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Push-Pull Structures Based on 2-Aryl/thienyl Substituted Quinazolin-4(3H)-ones and 4-Cyanoquinazolines

et al. 2022

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“…[28] Quinazoline chromophores have only been studied in recent years and their push-pull derivatives have mainly been based on quinazolin-2-yl and quinazolin-4-yl fragments. [35,[38][39][40][41][42][43] In particular, some of us have described a set of amino-substituted aryl-, styryl-, and arylethynylquinazolines. [44] It was found that all of these compounds exhibit emission quenching upon protonation.…”

Section: Introductionmentioning

confidence: 99%

Effect of protonation on the photophysical properties of 4-substituted and 4,7-disubstituted quinazoline push-pull chromophores

et al. 2021

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White-light emission from single molecular systems has attracted a great deal of attention due to their advantages over multicomponent emitters. Azaheterocyclic push-pull derivatives have been demonstrated to be white emitters by combining neutral and protonated forms in the appropriate ratio, although limited cases of white-light emission have been reported from quinazoline derivatives. Herein, we describe a series of push-pull 4-substituted and 4,7-disubstituted quinazolines that show white photoluminescence both in solution and in the solid state. All of the materials were prepared by straightforward Suzuki-Miyaura crosscoupling reactions and the compounds exhibited remarkable emission solvatochromism. In some cases the presence of acid prompted the appearance of emission bands of complementary colors. Thus, multicolor photoluminescence, including white light, could be finely tuned by the controlled protonation of the electron-deficient quinazoline ring.

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Methyl‐ and Methoxy‐substituted 2‐(Pyridin‐2‐yl)‐4‐(4‐aminophenyl)quinazolines: Synthesis and Photophysical Properties

Kopotilova,

Valieva,

Kudryashova

et al. 2024

Asian J Org Chem

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A series of 2‐(2‐pyridyl)quinazoline luminophores containing donor aryl fragment at position 4 and methyl or methoxy groups at benzene ring has been synthesized by efficient three‐step route. The linear optical properties have been studied by UV/Vis absorption and photoluminescence spectra in two solvents. We revealed that introduction of additional methyl group or the replacement of methyl substituents with methoxy ones lead to sequentially shift of absorption and emission maximum to blue region. 9H‐Carbazol‐9‐yl‐containing derivative is characterized by hypsochromically shifted absorption band compared to NEt2 and NPh2 counterparts. Unlike 9H‐carbazol‐9‐yl‐derivative, Et2N‐ and Ph2N‐bearing quinazolines demonstrate considerable decrease in quantum yield values when going from toluene to MeCN. Solvatochromic properties have been explored, the pronounced bathochromic shift was observed in fluorescence spectra with the increase of solvents polarity. Moreover, the compounds show significant shift of emission band with the increase of water fraction in DMSO/H2O mixture. Two‐photon optical properties were also studied, the two‐photon absorption cross‐sections in MeCN and toluene reached 120 GM and 210 GM, respectively. The presence of additional methyl group has little impact on δTPA, while introduction of methoxy substituents dramatically decreases TPA cross sections. Additionally, a quantum‐chemical calculations of synthesized compounds were performed to support the experimental data.

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Electron‐Withdrawing Substituted Quinazoline Push‐Pull Chromophores: Synthesis, Electrochemical, Photophysical and Second‐Order Nonlinear Optical Properties

Cited by 21 publications

References 71 publications

Push-Pull Structures Based on 2-Aryl/thienyl Substituted Quinazolin-4(3H)-ones and 4-Cyanoquinazolines

Push-Pull Structures Based on 2-Aryl/thienyl Substituted Quinazolin-4(3H)-ones and 4-Cyanoquinazolines

Effect of protonation on the photophysical properties of 4-substituted and 4,7-disubstituted quinazoline push-pull chromophores

Methyl‐ and Methoxy‐substituted 2‐(Pyridin‐2‐yl)‐4‐(4‐aminophenyl)quinazolines: Synthesis and Photophysical Properties

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