A unique small molecule class of fluorophores with large Stokes shift based on the electron deficient 9-methoxypyrroloisoquinolinetrione core

Khitrov, Michael D.; Platonov, Dmitry N.; Belyy, Aleksandr Yu.; Trainov, Konstantin P.; Velmiskina, Julia A.; Medvedev, Michael G.; Salikov, Rinat F.; Tomilov, Yu. V.

doi:10.1016/j.dyepig.2022.110344

Cited by 13 publications

(8 citation statements)

References 47 publications

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“…Notably, the Stokes shift are in the range of 8543–9265 cm −1 (Table 3); as expected, these values are higher to those obtained for the solutions of the complexes. The occurrence of such high values can be ascribed to a number of phenomena/ functions [37–44] . They indicate the aspects such as a fast relaxation from the initial state to the emissive state; the intramolecular energy transfer where some portion of the molecule acts as a donor, absorbing light, and another part serves as an acceptor; the change in the dipole moment which is the difference between ground and excited state dipole moment in polar surroundings [40–44] .…”

Section: Resultsmentioning

confidence: 99%

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Tris(boranil) Columnar Liquid Crystalline Fluorophores: pseudo‐Triphenylene Boron(III) Complexes with Peripheral N−B−O Linkages

Veerabhadraswamy

Khatavi

Rathod

et al. 2023

Chemistry A European J

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The borate complexes derived from salicylaldimine ligands, called boranils, possess a wide range of photophysical and electronic characteristics intrinsically. The unique combination of molecular rigidity, rendered by four-coordinate boron bridges, and extended π-conjugation enable them to serve as technically feasible fluorescent materials (dyes). The incorporation of liquid crystallinity in these boron(III) complexes, especially the columnar (Col) mesomorphism, which is overlooked hitherto, would provide a new dimension to these complexes. Herein, we report the first examples of tris(boranil) discotic liquid crystal (LC) dyes that have been readily synthesized by treating tris(Nsalicylideneaniline)s, (TSAN)s, with BF 3 .Et 2 O in the presence of an acid quencher. These C 3 -symmetric borate complexes selfassemble into the Col phase, existing over a wide thermal span including room temperature. The 2D periodic order of the Col phases shows dependence on the length of the peripheral tails. The photophysical measurements reveal the fluorescence emission in their two condensed states viz., solid and Col phase, and in solution. Their electrochemical, twostep oxidation process coupled with the aforesaid features upholds their significance in applied research.

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Section: Resultsmentioning

confidence: 99%

“…The occurrence of such high values can be ascribed to a number of phenomena/ functions. [37][38][39][40][41][42][43][44] They indicate the aspects such as a fast relaxation from the initial state to the emissive state; the intramolecular energy transfer where some portion of the molecule acts as a donor,…”

Section: Photophysical Propertiesmentioning

confidence: 99%

Tris(boranil) Columnar Liquid Crystalline Fluorophores: pseudo‐Triphenylene Boron(III) Complexes with Peripheral N−B−O Linkages

Veerabhadraswamy

Khatavi

Rathod

et al. 2023

Chemistry A European J

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“…Thus, the cracks in the SEM images (Figure 6b) can Of the starting compounds, only M exhibited noticeable fluorescence. Thus, it can be assumed that fluorescence in this system can arise for four reasons: (1) fluorescence due to the transition to another tautomeric form in the excited state [52,53]; (2) hydrogen atom transfer from TBA to M; (3) fluorescence of radical species; and (4) fluorescence on crystal defects [54].…”

Section: Resultsmentioning

confidence: 99%

Supramolecular Assemblies of Melamine-2-Thiobarbiturate and Melamine-Barbiturate-2-Thiobarbiturate: Experimental and Theoretical Studies

Moskalenko,

Shilovskikh,

Nesterov

et al. 2023

Crystals

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In this work, we considered the formation of supramolecular assemblies of melamine-thiobarbiturate and melamine-barbiturate-thiobarbiturate. It is known that thiobarbituric acid can form many tautomers, as well as different motifs due to the change of C2=O to C2=S hydrogen bonds. We formed the crystal. The resulting crystals were studied with scanning electron microscopy (SEM), optical fluorescence microscopy, single crystal and powder (PXRD) X-ray diffraction analyses, and solid state nuclear magnetic resonance (ss NMR). These systems were theoretically studied using density functional theory (DFT) and classical molecular dynamics (MD) simulations. Interestingly, just as in the case of melamine barbiturate, during the crystallization process, hydrogen from the C5 moiety of thiobarbituric acid migrates to the melamine molecule. In addition, the resulting melamine thiobarbiturate crystals exhibit fluorescence behavior in the red region (~565–605 nm), while the melamine barbiturate crystals are fluorescent in the green region (512–542 nm).

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“…It is also viable that the distortion of a seven-membered ring in HMCH is caused by steric hindrance of ester groups which can be disabled in the case of less sterically hindered substituents. Moreover, HMCH was found to exhibit unique reactivity under the action of various nucleophilic and electrophilic agents, yielding a number of functional materials with interesting properties, for example, large Stokes shift superphotoacidic fluorophores. − On the other hand, we have shown that other available cycloheptatrienes containing up to five electron-withdrawing groups neither form a stable anion nor exhibit chemical properties of HMCH . Thus, a new strategy for the synthesis of highly electron-deficient cycloheptatrienes will be of high demand from both theoretical and applicative points of view.…”

Section: Introductionmentioning

confidence: 99%

Cascade Vinylation/8π-Electrocyclization and Cu(II)-Catalyzed Dehydrogenation toward Highly Stable Formally Antiaromatic Cycloheptatrienyl Anions

et al. 2023

Self Cite

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An approach to the synthesis of seven-membered systems via the chain elongation of nucleophilic propenes and subsequent 8π-electrocyclization is proposed. The cascade reaction yields either cycloheptadienes or bicycloheptenes, and the latter are formed via a 6π-electrocyclization of intermediate cycloheptadienyl anion which was proved to be reversible in a basic medium. The electrocyclic nature of the ring-closing reactions was supported by density functional theory and DLPNO/CCSD(T) calculations. Highly electron-deficient cycloheptatrienes can be obtained from cycloheptadienes or bicycloheptenes via oxidation either introduced into the cascade reaction or performed as a separate reaction, with the overall yield of up to 81%. The oxidation step was performed by means of a rarely encountered Cu(II)-catalyzed dehydrogenation of cycloheptadienes or bicycloheptenes, and so the reaction mechanism was proposed. Stable formally 8π-antiaromatic cycloheptatrienyl-anion containing compounds were obtained, and some correlations between their UV−vis spectra and the structure of the distorted cycloheptatrienyl-anion moiety were clarified. Additionally, a base-induced retro-[2 + 2]-cycloaddition in a bicycloheptene derivative gave cyanotetra-(methoxycarbonyl)cyclopentadienyl cesium.

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A unique small molecule class of fluorophores with large Stokes shift based on the electron deficient 9-methoxypyrroloisoquinolinetrione core

Cited by 13 publications

References 47 publications

Tris(boranil) Columnar Liquid Crystalline Fluorophores: pseudo‐Triphenylene Boron(III) Complexes with Peripheral N−B−O Linkages

Tris(boranil) Columnar Liquid Crystalline Fluorophores: pseudo‐Triphenylene Boron(III) Complexes with Peripheral N−B−O Linkages

Supramolecular Assemblies of Melamine-2-Thiobarbiturate and Melamine-Barbiturate-2-Thiobarbiturate: Experimental and Theoretical Studies

Cascade Vinylation/8π-Electrocyclization and Cu(II)-Catalyzed Dehydrogenation toward Highly Stable Formally Antiaromatic Cycloheptatrienyl Anions

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