An Unusual Charge Umpolung:  Synthesis of the Bay Region Diketone 2,3:10,11-Dibenzoperylene-1,12-dione

Benshafrut, Ronnie; Hoffman, Ralph E.; Rabinovitz, Mordecai; Müllen, Kläus

doi:10.1021/jo981562s

Cited by 11 publications

(8 citation statements)

References 27 publications

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“…The π-π* transition in perylene and its substituted analogues has been used as a model for many photophysical studies [9–10], and this work is expanding as new perylene compounds are developed to optimize desirable photophysical properties. Perylene analogues with electron donating groups may provide favorable properties for photoactive dyes [11], but few have appeared in the literature with overall donating substituent effects [12–13]. …”

Section: Introductionmentioning

confidence: 99%

The photophysical characterisation of novel 3,9-dialkyloxy- and diacyloxyperylenes

et al. 2011

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The fundamental photophysical properties of three symmetrically substituted 3,9-perylene analogues were examined in a diverse range of solvents. All three compounds exhibited solvent-dependent fluorescence quantum yield, which was lower than that of perylene or its diimides. Whilst the absence of a large excited state dipole moment suggests that there is no preferential charge accumulation in one side of the molecules, the data suggest that intramolecular electron transfer occurs and that such an event causes additional photochemical mechanisms in chlorinated compounds where the fluorescence quantum yield is lower than in all other solvents and the values of the fluorescence decay change significantly. The dyes could be an interesting new class of fluorescence tags for labeling biomolecules and as dyes for organic photovoltaic materials.

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Section: Introductionmentioning

confidence: 99%

The photophysical characterisation of novel 3,9-dialkyloxy- and diacyloxyperylenes

et al. 2011

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“…Ever since correlation was demonstrated between calculated and experimental charge distributions—using Hückel molecular orbital (HMO) calculations and 1 H‐NMR,14 or complete neglect of differential overlap (CNDO) calculations, and 13 C‐NMR15—such auxiliary computations have become routine in explaining and predicting reactivity modes 16–18. Eliasson et al19 have further refined the relation between the change in 13 C‐NMR chemical shifts that occur upon reduction and the added charge ( K C ), by separating the effect of charge shielding from the anisotropy effect: where F C is the pure chemical shift/charge factor (estimated to be 134 ppm/ e − ), n C is the total number of carbon atoms in the π ‐system, and Q π is the total π ‐charge change (i.e., −2 for dianions).…”

Section: Characterization Of Polyarene Anionsmentioning

confidence: 99%

Polyarene anions: interplay between theory and experiment

Eisenberg¹,

Shenhar²

2011

WIREs Comput Mol Sci

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Polyarenes, or polycyclic aromatic hydrocarbons (PAHs), represent a ubiquitous and heavily studied type of compounds, appealing for their interesting spectroscopic, supramolecular, organometallic, and other properties. A major branch of research is concerned with polyarene anions: their electronic and structural properties, reactivity, aromaticity, and spectroscopy. This review describes the major role of computational investigations in complementing, explaining, and guiding experimental research, and thus providing invaluable contribution to our understanding of polyarene anions. The scope of this review focuses on polyarenes composed only from sp 2 -hybridized carbons and limits the discussion to the quantum-mechanical method of calculation. The topics covered include computation-assisted characterization; choice of methods; transformations induced by reduction, including anistropic charge redistributions, reorganization of bonding structure, flattening of curved polyarenes (buckybowls), and Jahn-Teller distortion; aromaticity topics such as ring currents and aromaticity measures; reactivity, for example, toward electrophilic substitution or ring closure, acidity and basicity, and self-assembly interactions in solution and in the gas phase; and finally, spectroscopy, mainly for astrochemical research, ranging from the mid-infrared to the far-ultraviolet spectral ranges. C 2011 John Wiley & Sons, Ltd.

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Section: Introductionmentioning

confidence: 99%

“…Almost nothing is known about the mechanistic details of this reaction. , Even the stoichiometry is uncertain, so the metal is generally just used in large excess. Because this reaction is so poorly understood and the yields rarely exceed 50%, the method remains underutilized in synthesis. The most prominent application is probably the syntheses of rylenes by Müllen et al, in which potassium metal was used to “zip up” specifically designed oligomers of 1,4-linked naphthalenes.…”

Section: Introductionmentioning

confidence: 99%

An Oxidation Induced by Potassium Metal. Studies on the Anionic Cyclodehydrogenation of 1,1′-Binaphthyl to Perylene

et al. 2010

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Oxidative cyclization of 1,1'-binaphthyl (1) to perylene (2) can be achieved in essentially quantitative yield by the action of three or more equivalents of potassium metal in hot tetrahydrofuran. An overall reaction mechanism is proposed that accounts for all of the experimental observations reported by previous investigators and those from the present studies. The trans-6a,6b-dihydroperylene dianion (6(2-)) is believed to be the pivotal intermediate from which H(2) is lost. A radical chain reaction involving free hydrogen atoms (H(•)) in the two-step propagation cycle is proposed to explain the formation of H(2) from 6(2-). Anionic cyclodehydrogenations of this sort are complementary to those performed under strongly acidic/oxidizing conditions, photochemically, or thermally (flash vacuum pyrolysis), and a better understanding of how they occur, together with the optimized synthetic protocol reported here, should encourage their wider use in organic synthesis.

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An Unusual Charge Umpolung: Synthesis of the Bay Region Diketone 2,3:10,11-Dibenzoperylene-1,12-dione

Cited by 11 publications

References 27 publications

The photophysical characterisation of novel 3,9-dialkyloxy- and diacyloxyperylenes

The photophysical characterisation of novel 3,9-dialkyloxy- and diacyloxyperylenes

Polyarene anions: interplay between theory and experiment

An Oxidation Induced by Potassium Metal. Studies on the Anionic Cyclodehydrogenation of 1,1′-Binaphthyl to Perylene

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