Vibrational OH-Stretching Overtone Spectroscopy of Jet-Cooled Resorcinol and Hydroquinone Rotamers

Hattori, Kaori; Ishiuchi, Shun‐ichi; Fujii, Minoru; Howard, Daryl L.; Kjaergaard, Henrik G.

doi:10.1021/jp071677c

Cited by 14 publications

(12 citation statements)

References 29 publications

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“…Actually, in both RE(I) and RE(II), only one OH band appeared at the same frequency at 3658 cm À1 in the observed spectra. 45 This result indicates that the coupling between the two OH groups is very weak, which is also supported in the calculated spectra of Fig. 2(k).…”

Section: Resultssupporting

confidence: 76%

“…The OH bands of trans-and cis-HQ appear at 3662 and 3663 cm À1 , respectively. 45 In HQ, the two OH groups are symmetrically equivalent in the two conformers. So, the observed IR band is assigned to the antisymmetric OH stretching vibration in trans-HQ, while the symmetric and antisymmetric OH stretching vibrations are thought to be overlapped in cis-HQ.…”

Section: Resultsmentioning

confidence: 99%

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Cage effects on conformational preference and photophysics in the host–guest complex of benzenediols with 18-Crown-6

Morishima

Kusaka

Inokuchi

et al. 2016

Phys. Chem. Chem. Phys.

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The conformational preference and modification of photophysics of benzenediols, namely hydroquinone (HQ), resorcinol (RE) and catechol (CA), upon host-guest complex formation with 18-Crown-6 (18C6) have been investigated, under supersonically jet-cooled conditions. Laser induced fluorescence (LIF) and UV-UV hole-burning spectra indicate the presence of two conformers for HQ and RE and one conformer for CA. On the other hand, the number of isomers is reduced to one in the 18C6·HQ and 18C6·RE complexes, while the 18C6·CA complex has three stable isomers. The IR spectra of the OH stretching vibration reveal that the two OH groups are H-bonded in 18C6·CA and 18C6·RE. In 18C6·RE, RE adopts the highest energy conformation in the bare form. In 18C6·HQ, the H-bonding of one OH group affects the orientation of the other OH group. The complex formation changes the photophysics of the S1 state of the benzenediols in a different manner. In our previous work, we reported a remarkable S1 lifetime elongation in 18C6·CA complexes; the S1 lifetime of CA is elongated more than 1000 times longer (8 ps → 10.3 ns) in 18C6·CA (F. Morishima et al., J. Phys. Chem. B, 2015, 119, 2557-2565), which we called the "cage effect". In 18C6·RE, the increase of S1 lifetime is moderate: 4.0 ns (monomer) → 10.5 ns (complex). On the other hand, the S1 lifetime of HQ is shortened in 18C6·HQ: 2.6 ns (monomer) → 0.54 ns (complex). Density functional theory (DFT) calculations suggest that these behaviors are related to the S1 ((1)ππ*)-(1)πσ* energy gap, the character of the S2 state and the symmetry of benzenediol. These experimental results clearly show the potential ability of 18C6 to control the conformation and modification of the electronic structure of guest species.

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Section: Resultssupporting

confidence: 76%

Section: Resultsmentioning

confidence: 99%

Cage effects on conformational preference and photophysics in the host–guest complex of benzenediols with 18-Crown-6

Morishima

Kusaka

Inokuchi

et al. 2016

Phys. Chem. Chem. Phys.

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“…We then considered the optimized configurations of resorcinol, R . Various experimental − and theoretical studies − have been carried out to determine the configuration of R and, in particular, the relative orientation of the two hydroxyl groups. Figure shows the optimized configurations at the B3LYP/6-311G(2d,d,p) level of theory along with the relative energies at the CBS-QB3 level for the three possible conformers.…”

Section: Resultsmentioning

confidence: 99%

Theoretical Study on Reaction Pathways Leading to CO and CO₂ in the Pyrolysis of Resorcinol

et al. 2017

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Possible pathways for the pyrolysis of resorcinol with the formation of CO and CO as final products were proposed and evaluated using ab initio calculations. Our experimental study revealed that large quantities of CO are generated in the pyrolysis of 1,3-dihydroxybenzene (resorcinol), while the pyrolysis of the dihydroxybenzene isomers 1,2-dihydroxybenzene (catechol) and 1,4-dihydroxybenzene (hydroquinone) produces little CO. The fate of oxygen atoms in catechol and hydroquinone was essentially the formation of CO. In the proposed pathways, the triplet ground state m-benzoquinone was generated initially from simultaneous cleavage of the two O-H bonds in resorcinol. Subsequently, the direct cleavage of a C-C bond of the m-benzoquinone diradical yields 2-oxidanylcyclopenta-2,4-dien-1-yl-methanone, which can be converted via two channels: release of CO from the aldehyde radical group and combination of the ketone radical and carbon atom in the aldehyde radical group to form the 6-oxabicyclo[3.2.0]hepta-2,4-dien-7-one, resulting in the release of CO. Potential energy surfaces along the proposed reaction pathways were calculated employing the CBS-QB3 method, and the rate constants at the high-pressure limit were also evaluated based on transition-state theory to assess the feasibility of the proposed reaction pathways.

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“…Briefly, Rs has two OH groups, resulting in three rotamers RsI, RsII, and RsIII, according to their orientation (Figure ). RsI and RsII have comparable stability, and both are observed in a cold molecular beam. − RsIII is the least stable and has been found only at higher temperature . The formation of clusters with Ar requires low temperature, and thus only RsI–Ar n and RsII–Ar n are observed in a molecular beam .…”

Section: Introductionmentioning

confidence: 99%

Ionization-Induced π → H Site Switching in Resorcinol–Ar_n (n = 1 and 2) Clusters Probed by Infrared Spectroscopy

et al. 2019

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Infrared (IR) spectra of resorcinol (Rs)−Ar n clusters (n = 1 and 2) have been measured in the neutral and cationic ground states (S 0 and D 0 ) by IR dip and resonanceenhanced multiphoton ionization (REMPI)-IR spectroscopy. The OH stretching vibrations in S 0 keep their frequency regardless of the number of Ar atoms and the conformation of the OH groups in Rs (rotamers RsI and RsII), demonstrating that the Ar atoms are attached to the aromatic π-ring (π-bound structure) in S 0 . In the D 0 state, the IR spectra of Rs + −Ar n reflect the difference in the Rs conformations (RsI + and RsII + ). For n = 1, the IR spectra of both rotamers are almost the same as those of the corresponding monomer cations, indicating that Ar ligands essentially remain π-bonded after ionization. In contrast, the IR spectra of Rs + −Ar 2 show hydrogen-bonded and free OH stretching vibrations, demonstrating that for a significant fraction of the clusters, the Ar atoms migrate from the π-bound site to the OH groups. The ionization-induced π → H migration yields are not unity for both rotamers RsI + −Ar 2 and RsII + −Ar 2 . This result is in sharp contrast to phenol + −Ar 2 , in which one of the Ar atoms migrates to the OH site with 100% yield. The mechanism leading to the nonunity yield in Rs + −Ar 2 is discussed in terms of the number of OH binding sites and Franck−Condon factors. The ionization excess energy dependence of the IR spectra of Rs + −Ar 2 and its Rs + −Ar fragments is discussed in terms of the Ar binding energies estimated from the photoionization and photodissociation efficiency spectra.

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Vibrational OH-Stretching Overtone Spectroscopy of Jet-Cooled Resorcinol and Hydroquinone Rotamers

Cited by 14 publications

References 29 publications

Cage effects on conformational preference and photophysics in the host–guest complex of benzenediols with 18-Crown-6

Cage effects on conformational preference and photophysics in the host–guest complex of benzenediols with 18-Crown-6

Theoretical Study on Reaction Pathways Leading to CO and CO₂ in the Pyrolysis of Resorcinol

Ionization-Induced π → H Site Switching in Resorcinol–Ar_n (n = 1 and 2) Clusters Probed by Infrared Spectroscopy

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Vibrational OH-Stretching Overtone Spectroscopy of Jet-Cooled Resorcinol and Hydroquinone Rotamers

Cited by 14 publications

References 29 publications

Cage effects on conformational preference and photophysics in the host–guest complex of benzenediols with 18-Crown-6

Cage effects on conformational preference and photophysics in the host–guest complex of benzenediols with 18-Crown-6

Theoretical Study on Reaction Pathways Leading to CO and CO2 in the Pyrolysis of Resorcinol

Ionization-Induced π → H Site Switching in Resorcinol–Arn (n = 1 and 2) Clusters Probed by Infrared Spectroscopy

Contact Info

Product

Resources

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Theoretical Study on Reaction Pathways Leading to CO and CO₂ in the Pyrolysis of Resorcinol

Ionization-Induced π → H Site Switching in Resorcinol–Ar_n (n = 1 and 2) Clusters Probed by Infrared Spectroscopy