Vibrational assignments in the 288 nm electronic absorption spectrum of styrene: New information on the C(1)-C(α) torsional vibrational levels in the ground electronic state of styrene, styrene-β-D2, and p-fluorostyrene

Hollas, J. Michael; KHALILIPOUR, E.; Thakur, Surya N.

doi:10.1016/0022-2852(78)90218-7

Cited by 78 publications

(48 citation statements)

References 31 publications

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“…C remains as a conformational indicator. Now, although styrene is probably planar in the ground state (43,44), the present compounds most likely are not, the a substituents entailing destabilization of a coplanar arrangement of the benzene and olefinic moieties. Furthermore, the internal rotational potential may not be twofold.…”

Section: Cchmentioning

confidence: 86%

“…The assumption of a twofold internal barrier, together with the harmonic approximation for the torsion about the exocyclic bond, leads to a Vz of 0.5 or 1.0 kcal/mol from the microwave spectrum (44) of 4-fluorostyrene, and 1.0 kcal/mol from vibrational assignments in the 288-nm absorption spectrum (43). Heat capacity data (47) give Vz as 2.87 kcal/mol.…”

Section: Cchmentioning

confidence: 99%

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The conformational dependence of in some 4-fluorophenyl derivatives of methane, ethene, and cyclohexane

Schaefer¹,

Peeling²,

Penner³

et al. 1985

Can. J. Chem.

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The spin-spin coupling over six bonds between '"F and "C nuclei on the sidechain in thirteen 4-fluorophenyl derivatives appears to be mediated by a a-.rr mechanism. Its magnitude depends somewhat on the hybridization state of the carbon atom canying the coupled nucleus, as well as on the electronegativity of substituents attached to this carbon atom. A consistent behaviour of this coupling is observed if its value is assumed to be proportional to sin2 0, where 0 is the angle by which the bond canying the coupled carbon nucleus twists out of the ring plane. However, in 4-fluorostyrene 'J%" is a -rr electron coupling in the planar form, so that its magnitude decreases as the vinyl group twists out of the benzene plane. The a--rr contribution to this coupling is smaller than the -rr component. IntroductionIn the study of long-range spin-spin coupling constants, their mechanisms, and their application to conformational problems (1-16), it has been shown ( 5 ) that 6~:.CH varies as sin2 0 in toluene derivatives. Here 0 is the angle by which the a C-H bond twists out of the benzene plane. The coupling proceeds via a u-.rr mechanism and involves the sidechain proton and the para ring proton. Similarly, S~;,CH, the coupling between the sidechain proton and the para carbon-13 nucleus also varies as sin2 0 (17,18), implying that this parameter allows an extension (8) of the J method (I) as a conformational

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Section: Cchmentioning

confidence: 86%

Section: Cchmentioning

confidence: 99%

The conformational dependence of in some 4-fluorophenyl derivatives of methane, ethene, and cyclohexane

Schaefer¹,

Peeling²,

Penner³

et al. 1985

Can. J. Chem.

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“…[10][11][12] Phosphorescence has never been detected from photoexcited styrene; however, many studies have suggested that photochemical cis-trans isomerisation mechanisms for styrene proceed via triplet states. 11,[13][14][15] known to have a nanosecond timescale.…”

Section: Introductionmentioning

confidence: 99%

Ultrafast dynamics through conical intersections and intramolecular vibrational energy redistribution in styrene

Nunn

Minns

Spesyvtsev

et al. 2010

Phys. Chem. Chem. Phys.

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We report a femtosecond time-resolved photoelectron spectroscopy (TRPES) investigation of internal conversion in the first two excited singlet electronic states of styrene. We find that radiationless decay through an S 1 /S 0 conical intersection occurs on a timescale of ~4 ps following direct excitation to S 1 with 0.6 eV excess energy, but that the same process is significantly slower (~20 ps) if it follows internal conversion from S 2 to S 1 after excitation to S 2 with 0.3 eV excess energy (0.9 eV excess energy in S 1 ).

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“…Beside the shift of the electronic transition energy, the emission properties of [Pt(bpy-ds)2] 2+ exhibit further changes with respect to [Pt(bpy-hs)2] 2+. Similar effects are well known and are usually observed upon deuteration of emitting centers (e.g., see [37,44,60,74,85,[102][103][104][105][106][107]). In particular, (1) all vibrational energies are red-shifted.…”

Section: Emission Properties Of [Pt(bpy-ds)2] 2+ and [Pt(bpy-hs)(bpy-mentioning

confidence: 56%

“…Moreover, if specific positions or spatial regions of the compound are isotopically designated, one may even obtain information about the spatial spread of the wave functions involved in the emission process. Similar investigations have already been carried out for organic molecules [74,102,103] as well as for transition metal complexes [44,60,74,85,104]. Here, we focus on [Pt(bpy-ds)2] 2+ and [Pt(bpy-hs)(bpy-ds)] 2+.…”

Section: Emission Properties Of [Pt(bpy-ds)2] 2+ and [Pt(bpy-hs)(bpy-mentioning

confidence: 95%

Characterization of excited electronic and vibronic states of platinum metal compounds with chelate ligands by highly frequency-resolved and time-resolved spectra

Yersin

Humbs

Strasser

Topics in Current Chemistry

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The lowest excited electronic states of triplet character and related vibronic properties are discussed in detail on the basis of highly frequency-resolved and time-resolved emission and excitation spectra of per-protonated, per-deuterated, and partially deuterated [Pt(bpy)2] 2+, [Rh(bpy)3] 3+, [Ru(bpy)3] 2+, and [Os(bpy)3] ~+. Emphasis is placed on the use of the enormous amount of information displayed in well-resolved vibrational satellite structures. For comparison, IR data and Raman spectra are also used. In addition, data are given for [Ru(bpz)Pt(3-thpy) 2, Pt(2-thpy)(CO)(Cl), Pt(2-thpy) 2, Pt(qol)2, Pt(qtl)2. Trends and effects are also addressed, which are related to the amount of metal d-orbital mixing. In particular, we discuss the role of traps and sites in the context of high-resolution, site-selective, and line-narrowed spectra of chromophores doped into matrices; the interplay between states of ligand-centered 3rtrr* and ~MLCT character; localization versus delocalization behavior; radiative decay properties; zero-field splittings; spin-lattice relaxations via direct and Orbach mechanisms; Arrhenius behavior after time delay; Franck-Condon activities and Huang-Rhys factors; Franck-Condon versus Herzberg Teller activities and tunability of these activities under high magnetic fields; isotope marking and deuteration effects; aggregate formation of [Ru(bpy)3]2+; and radiationless energy transfer in neat [Ru(bpy)3](PF6) 2. These effects are in part treated in detail, but the aim is to use easy-to-follow descriptions. In particular, it is emphasized throughout this review that chemical tunability opens fascinating possibilities for controlled variation of physical properties.

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Vibrational assignments in the 288 nm electronic absorption spectrum of styrene: New information on the C(1)-C(α) torsional vibrational levels in the ground electronic state of styrene, styrene-β-D2, and p-fluorostyrene

Cited by 78 publications

References 31 publications

The conformational dependence of in some 4-fluorophenyl derivatives of methane, ethene, and cyclohexane

The conformational dependence of in some 4-fluorophenyl derivatives of methane, ethene, and cyclohexane

Ultrafast dynamics through conical intersections and intramolecular vibrational energy redistribution in styrene

Characterization of excited electronic and vibronic states of platinum metal compounds with chelate ligands by highly frequency-resolved and time-resolved spectra

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