Steric Effects and Spectra in the Tetracyclones

Shapiro, Elliot L.; Becker, Ernest I.

doi:10.1021/ja01115a045

Cited by 12 publications

(11 citation statements)

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“…The electronic properties of the Tetraphenylcyclopentadienone and its derivatives obtained from the deliberate modification on the phenyl rings were previously reported 30–34 . These derivatives are subsequently utilized as synthetic intermediates for the production of polyphenylene dendrimers as well as building blocks for gelators that absorb and emit within the UV-visible frequencies 35–43 .…”

Section: Introductionmentioning

confidence: 99%

Tuning of the Electro-Optical Properties of Tetraphenylcyclopentadienone via Substitution of Oxygen with Sterically-Hindered Electron Withdrawing Groups

Coluccini

Anusha

Chen

et al. 2019

Sci Rep

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In this report, the substitution of the oxygen group (=O) of Tetraphenylcyclopentadienone with =CR 2 group (R = methyl ester or nitrile) was found to have tuned the electro-optical properties of the molecule. Although both groups are electrons withdrawing in nature, their absorption from UV-vis spectra analysis was observed to have been blue-shifted by methyl ester substitution and red-shifted by nitrile substitution. Interestingly, these substitutions helped to enhance the overall intensity of emission, especially in the context of methyl ester substitution whereby the emission was significantly boosted at higher concentrations due to hypothesized restrictions of intramolecular motions. These observations were explained through detailed descriptions of the electron withdrawing capability and steric properties of the substituents on the basis of density functional theory calculations.

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Section: Introductionmentioning

confidence: 99%

Tuning of the Electro-Optical Properties of Tetraphenylcyclopentadienone via Substitution of Oxygen with Sterically-Hindered Electron Withdrawing Groups

Coluccini

Anusha

Chen

et al. 2019

Sci Rep

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“…Absorption spectra of TACPD derivatives have been studied since the 1950s. [ 1,3,4 ] At first, the question about TACPDs was how various electron‐donating and electron‐withdrawing substituents affected their colour. Recent studies have employed modern computational methods to better understand the bonding of TACPDs so that they can potentially be incorporated into microscale electronics.…”

Section: Resultsmentioning

confidence: 99%

“…In chloroform, this peak was observed at 530 nm, in dioxane at 504 nm, and in benzene at 512 nm. [ 1,7,21 ] The excited state of this charge transfer transition is theorized to be the antiaromatic dipolar structure shown in Figure 2. [ 1,8,9 ] The electron‐withdrawing substituents in 2 – 4 caused this band to blue shift when compared with 1 , pointing to their destabilizing effects on this transition.…”

Section: Resultsmentioning

confidence: 99%

“…[ 1,7,21 ] The excited state of this charge transfer transition is theorized to be the antiaromatic dipolar structure shown in Figure 2. [ 1,8,9 ] The electron‐withdrawing substituents in 2 – 4 caused this band to blue shift when compared with 1 , pointing to their destabilizing effects on this transition. There was little variation in the wavelength of this absorption in 2 – 4 , pointing to a similarity in the effect of their substituents on the energetics of this transition.…”

Section: Resultsmentioning

confidence: 99%

“…Tetraarylcyclopentadienones (TACPDs) have been synthesized and their properties explored since the 1930s. [ 1,2 ] Their most striking feature is their intense colour, which ranges from deep maroon to a velvety dark purple, to almost black. This deep coloration was likely to have been what spurred their first photophysical studies, whose goal was to correlate changes in aryl ring substituents to changes in absorption spectra.…”

Section: Introductionmentioning

confidence: 99%

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Investigating the change in the photophysical properties of a trio of tetraphenylcyclopentadienone derivatives with varied groups on the aromatic rings in the 3‐ and 4‐positions

et al. 2020

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Organic compounds with electronic properties, such as a small band gap, are useful in areas ranging from organic field effect transistors to solar cells. Such organic compounds can possess conjugation and/or aromatic systems, with one example being tetraphenylcyclopentadienone and its derivatives. A trio of dramatically coloured tetraphenylcyclopentadienone derivatives with varied substituents on the aromatic rings in the 3‐ and 4‐positions were prepared. Their identities were confirmed using the usual methods, for example 1H nuclear magnetic resonance (NMR) spectroscopy, and their purity quantified using elemental analysis. The X‐ray crystal structure of compound 2 was determined. Its notable structural features involved the cyclopentadienone core with its distinct C−C and C=C bond lengths and its overall nonplanarity, both of which served to mitigate its antiaromatic nature. Chloroform solutions of compounds 2–4 exhibited absorption spectra with three absorption bands at approximately 250, 350, and 500 nm that were assigned to (π)→(π*) transitions. Computational chemistry methods assisted in assigning the observed transitions to a specific molecular orbital combination in the structures of 2–4. Emission in the red end of the visible spectrum (550–625 nm) was observed from chloroform solutions of all three of the prepared compounds.

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Ringverengung bei der Oxidation von phenyl‐substituierten Resorcinen

1967

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Beim Behandeln von (2) und (3) mit methanolisch r 0,Ol N NaOCH3-Losung erfolgt durch einen neuartigen Peresterzerfall ein Zuckerabbau. Der anomale Peroxyester (3) ist bei Raumtemperatur nach 5 Std. voltig zerfallen; es entstehen 70 % D-Arabinose (kristallin, papierchromatographisch rein), 66 % Kohlendioxid, tert.-Butanol und Essigsauremethylester. Als Nebenprodukt entstehen 30 % D-Gluconsaure-methylester. Die vollige Zersetzung des normalen Peroxyesters (2) erfordert energischere Bedingungen. Nach achtstundigem Erwarmen auf 60 "C werden 51 % D-Arabinose isoliert. Die Bis-peroxyester (4) und (5) werden durch Natriummethylat-Losung nicht unter C-C-Spaltung abgebaut ; es tritt lediglich Umesterung und Entacetylierung zum Schleimsaure-dimethylester (90 %) ein. Wir deuten den Zerfall von (3) als Fragmentierung [31 einer intermediar gehildeten pyranoiden Zwischenstufe (6). Vermutlich zerfallt auch (2) uher ein cyclisches Zwischenprodukt. CdHs CHj CH, Eingegangen am 19. Mai und 18. August 1967 [Z 600bl C6Hs CH, CH,

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Steric Effects and Spectra in the Tetracyclones

Cited by 12 publications

References 1 publication

Tuning of the Electro-Optical Properties of Tetraphenylcyclopentadienone via Substitution of Oxygen with Sterically-Hindered Electron Withdrawing Groups

Tuning of the Electro-Optical Properties of Tetraphenylcyclopentadienone via Substitution of Oxygen with Sterically-Hindered Electron Withdrawing Groups

Investigating the change in the photophysical properties of a trio of tetraphenylcyclopentadienone derivatives with varied groups on the aromatic rings in the 3‐ and 4‐positions

Ringverengung bei der Oxidation von phenyl‐substituierten Resorcinen

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