Spectroscopy of phenylcyclopropanes and phenylethanes. Unusual emissions from phenylcyclopropanes

Becker, Ralph S.; Edwards, L. A.; Bost, Robert O.; Elam, M.; Griffin, G. W.

doi:10.1021/ja00774a004

Cited by 31 publications

(19 citation statements)

References 8 publications

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“…The electronic absorption spectra of 1B were calculated by TD-DFT-B3LYP (-B97D) with 25 lowest singlet states. The calculated wavelengths of main UV-vis absorption peaks (simulated by B97D, about 277.58 and 217.88 nm) were only about 1 and 12 nm differences compared to the experimental results, [27,28] which demonstrated that B97D was a suitable method for cyclopropane derivatives. However, B3LYP overestimated the excitation energies.…”

Section: Theoretical Evidence and Computational Detailsmentioning

confidence: 72%

Theoretical Study of σ-π Conjugated Semiconductors Based on cis- and trans-Cyclopropane Derivatives

Liu¹,

Yang²,

Zhang³

et al. 2015

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The high strain cyclopropane as σ block model inserted in organic semiconductors to tune the structures and optical properties was investigated by the density functional theory method. The band gaps and absorption peaks of 1,2-disubstituted cyclopropanes were between the corresponding alkanes and olefins. The cis-isomers had higher steric strain between two substituents and lower symmetry than the trans-isomers in ground-state structures. The electronic transitions (S 0 →S 1 ) were mainly on the aryl parts, which were stronger coherence with surrounding atoms in cis-isomers, while the trans-isomers were on the cyclopropyl. Furthermore, 1,2-disubstituted cyclopropanes (1A, 1B, 2A, 4B) could respond to the charge stimulation, which are potential materials for organic electronics and mechatronics.

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Section: Theoretical Evidence and Computational Detailsmentioning

confidence: 72%

Theoretical Study of σ-π Conjugated Semiconductors Based on cis- and trans-Cyclopropane Derivatives

Liu¹,

Yang²,

Zhang³

et al. 2015

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“…Bibenzyl modes, on the other hand, experience little enhancement because the excited electronic states of bibenzyl are much higher in energy than those of DPOT. 38 From this series of 2/4 scans, the DPOT 1150 cm Ϫ1 resonance was referenced to the bibenzyl 1200 cm Ϫ1 resonance. The ratio of peak areas was measured in this case because the DPOT 1150 cm Ϫ1 line is broad ͑FWHMϷ6 cm Ϫ1 ͒ and no doubt comprises more than one resonance and perhaps overlapping sites.…”

Section: Site-selective Fluorescence and Fluorescence Excitation Specmentioning

confidence: 99%

Multiresonant four-wave mixing in diphenyloctatetraene doped bibenzyl crystals

Hawi

Wright

1995

The Journal of Chemical Physics

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A diphenyloctatetraene ͑DPOT͒ doped bibenzyl crystal is a model system for studying the spectroscopic properties of polyenes because the well-defined local environment of the DPOT eliminates most of the inhomogeneous broadening that obscures many transitions. The spectra of the three DPOT sites in this host are measured with site-selective laser spectroscopy to define the vibrational, electronic, and vibronic states of the S 0 , S 1 , and S 2 electronic states. Multiply resonant four-wave mixing spectra were then obtained using a coherent anti-Stokes Raman spectroscopy method ͑CARS͒ for a series of different laser frequencies in order to define the CARS excitation profile ͑CEP͒. The CEP profile of the CvC and C-C stretch vibrations showed strong enhancement of the four-wave mixing from the S 2 state but only the CvC stretch mode had observable enhancement from the S 1 state. Contrary to previous studies in pentacene, azulene, and perylene, DPOT did not exhibit enhancement of vibronic transitions that would permit mode selective or site-selective nonlinear spectroscopy.

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“…Photoreactions of 1,2‐diphenylcyclopropanes ( 1 ), reported by Becker and Ramamurthy, also display “unusual” luminescence behavior associated with excited state biradical generation by photoinduced C–C bond cleavage (Scheme A) . Although many mechanistic studies of this photoreaction have been performed, the detailed mechanism still remains unclear.…”

Section: Introductionmentioning

confidence: 99%

Adiabatic process of higher electronically excited states: luminescence from an excited state biradical generated by irradiation of benzophenone‐substituted cyclopropanes

Matsui

Oishi

Ohta

et al. 2016

J of Physical Organic Chem

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Adiabatic photochemical reactions of cyclopropanes possessing a benzophenone moiety (trans‐ and cis‐5), which generate a luminescent excited biradical 16••*, were studied. Various photochemical and spectroscopic techniques were used for this purpose. Excitation (350 nm, n,π* band) of 5 at 77 K affords the lowest excited state 15* that undergoes intersystem crossing to form 35*, which deactivates through phosphorescence. In contrast, 295‐nm excitation (π,π* band) of 5 affords the higher electronically excited state 15**, which undergoes adiabatic C–C bond cleavage reaction to form the excited biradical 16••* that luminesces at 630 nm. The results suggest that 5 follows 2 photoreaction modes depending on the excitation wavelength, a finding that disobeys Kasha's rule.

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Spectroscopy of phenylcyclopropanes and phenylethanes. Unusual emissions from phenylcyclopropanes

Cited by 31 publications

References 8 publications

Theoretical Study of σ-π Conjugated Semiconductors Based on cis- and trans-Cyclopropane Derivatives

Theoretical Study of σ-π Conjugated Semiconductors Based on cis- and trans-Cyclopropane Derivatives

Multiresonant four-wave mixing in diphenyloctatetraene doped bibenzyl crystals

Adiabatic process of higher electronically excited states: luminescence from an excited state biradical generated by irradiation of benzophenone‐substituted cyclopropanes

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Spectroscopy of phenylcyclopropanes and phenylethanes. Unusual emissions from phenylcyclopropanes

Cited by 31 publications

References 8 publications

Theoretical Study of &sigma;-&pi; Conjugated Semiconductors Based on cis- and trans-Cyclopropane Derivatives

Theoretical Study of &sigma;-&pi; Conjugated Semiconductors Based on cis- and trans-Cyclopropane Derivatives

Multiresonant four-wave mixing in diphenyloctatetraene doped bibenzyl crystals

Adiabatic process of higher electronically excited states: luminescence from an excited state biradical generated by irradiation of benzophenone‐substituted cyclopropanes

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Theoretical Study of σ-π Conjugated Semiconductors Based on cis- and trans-Cyclopropane Derivatives

Theoretical Study of σ-π Conjugated Semiconductors Based on cis- and trans-Cyclopropane Derivatives