Push–pull dyes containing malononitrile dimer as acceptor: synthesis, spectroscopy and quantum chemical calculations

Zerner, Michael C.; Reidlinger, Claudia; Fabian, Walter M. F.; Junék, H.

doi:10.1016/s0166-1280(00)00851-4

Cited by 21 publications

(8 citation statements)

References 56 publications

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“…From previous experiments [3], we expected quite good agreement between calculated and experimental absorption maxima. There is, however, one notable exception: the donor properties of amino groups, and, hence, the bathochromic shift induced (8, 17 ± 19), are greatly underestimated by the ZINDO procedure [11]. Apart from these limitations in terms of accuracy, one should see a general trend for the calculated absorption data and fairly good agreement with experimentally determined values.…”

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confidence: 73%

“…2-Methoxy-4-nitroaniline (10) served as the starting material for the desired derivatives 11 ± 13 by straightforward alkylation (Scheme 2). It turned out that NaH and Me 2 SO 4 were optimal for monomethylation, which can be run at moderate temperatures without occurrence of significant double alkylation (11). The N,N-dimethylaniline derivative 13 could be obtained with MeI and excess NaH.…”

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confidence: 99%

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A Combined Experimental and Theoretical Approach toward the Development of Optimized Luminescent Carbostyrils

Strohmeier

Fabian

Uray

2004

Helvetica Chimica Acta

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The synthesis and photophysical data of new carbostyrils (quinoline-2(1H)-ones) with the longest hitherto observed absorption-and emission wavelengths are described. Introduction of 6-amino, 7-MeO, and 4-(CF 3 ) substituents enabled us to rise the absorption and fluorescence maxima up to 414 and 557 nm, respectively. Supported by semi-empirical and ab initio calculations, the 6,7-(1,4-diazine)-fused carbostyril 23b displayed absorption maxima at up to 440 nm, with quantum yields of up to 0.9 and large Stokes shifts (> 100 nm), comparable to the best coumarin chromophores known. The new fluorophore is neither pH-sensitive between pH 6 and 10 nor susceptible to O 2 quenching. At pH 3, the emitted light appears greenish-white, which arises from three different stages of protonation.Introduction. ± In contrast to the coumarins ubiquitously used as fluorescent dyes [1], less attention has been paid to the aza-analogues quinolin-2(1H)-ones (carbostyrils), probably because of their lower extinction coefficients, hypsochromic absorption maxima, and more-cumbersome tuning of photophysical properties. However, carbostyrils are, in most cases, more resistant against pH changes (ring opening) and bleaching caused by chemical or thermal tackles. Nonetheless, 7-acetamido derivatives of Carbostyril-124, which absorb at ca. 335 nm and emit near 370 nm, have found applications in fluorescence analysis, as well as in −antenna-sensitized× europium luminescence [2]. The preference of a 7-amino group as auxochrome has its origin in the corresponding highly esteemed coumarin analogues.In earlier work [3], we have investigated substituent effects in all positions of the carbostyril system, which has provided fundamental data regarding their photophysical properties. Introduction of electron-donating and electron-accepting groups at certain positions does improve their spectral and luminescent characteristics. This converged to a so-called −push-pull× model with two electron-donating substituents in positions 6 and 7, and a CF 3 group as the acceptor at C(4). As a result of these systematic investigations, we developed 6,7-dimethoxy-4-(trifluoromethyl)quinolin-2(1H)one (1), which has an absorption maximum at 370 nm, a quantum yield of ca. 0.5, and a Stokes shift of ca. 70 nm). Inspired by this promising result, we sought further improvements [4], especially to break through the visible barrier for the absorption wavelength of carbostyrils, thus opening the field for new applications, because adequately priced light-emitting diodes (LEDs) as new excitation sources at 370, 405, and 430 nm have become available [5].Apart from the desired photophysical properties, our new fluorophores should also be readily accessible by simple chemical transformations. We envisaged to synthesize

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confidence: 73%

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confidence: 99%

A Combined Experimental and Theoretical Approach toward the Development of Optimized Luminescent Carbostyrils

Strohmeier

Fabian

Uray

2004

Helvetica Chimica Acta

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“…These structural features closely agree with the results of ab initio calculations on similar compounds bearing substituted benzylidene groups instead of the 1,3-dithiol-2-ylidene moiety. 13 In a similar vein, compound 10 also adopts conformation b (0.96 kcal/mol more stable than a), with a dihedral angle τ (C1-C2-C3-C4) = 43.2°. Nevertheless, the difference between the energy of the two conformers is small and the more polar conformer a can be the favored one in a polar environment, such as that found in the solid state.…”

Section: The Influence Of the Solventmentioning

confidence: 91%

Push-pull 1,4-dithiafulvenes: a combined experimental and theoretical study

Andreu¹,

Cerdán²,

Garı́n³

et al. 2003

Arkivoc

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“…43 In addition, some push-pull compounds found application in metal-free photoredoxcatalysis. [44][45] The main donor-acceptor (D-A) interaction in the compounds of type 14 is presumably happening between the malononitrile group, which is widely considered one of the strongest natural electron-withdrawing groups in organic chemistry, [45][46] and the proaromatic electron-donor 2-methylene-2,3-dihydro-1H-imidazole. This group is comparable to the widely explored 1,3-dithiol-2-ylidene (dithiafulvene).…”

Section: Functionalization Of the Heterocyclic Scaffoldmentioning

confidence: 99%

Selective functionalization of the 1H-imidazo[1,2-b]pyrazole scaffold. A new potential non-classical isostere of indole and a precursor of push–pull dyes

et al. 2021

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Push–pull dyes containing malononitrile dimer as acceptor: synthesis, spectroscopy and quantum chemical calculations

Cited by 21 publications

References 56 publications

A Combined Experimental and Theoretical Approach toward the Development of Optimized Luminescent Carbostyrils

A Combined Experimental and Theoretical Approach toward the Development of Optimized Luminescent Carbostyrils

Push-pull 1,4-dithiafulvenes: a combined experimental and theoretical study

Selective functionalization of the 1H-imidazo[1,2-b]pyrazole scaffold. A new potential non-classical isostere of indole and a precursor of push–pull dyes

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