Photoinduced rotational isomerization mechanism of 2-chlorobenzaldehyde in low-temperature rare-gas matrices by vibrational and electronic spectroscopies

Akai, Nobuyuki; Kudoh, Shinzoh; Takayanagi, Motowo; Nakata, Munetaka

doi:10.1016/s1010-6030(02)00135-1

Cited by 22 publications

(11 citation statements)

References 23 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In the infrared spectrum obtained after deposition, strong bands were observed at 1710 and 1705 cm −1 , which can be assigned to C=O stretching vibration of anti-CBA [10]. Fig.…”

Section: Photolysis Of Cba In the Ar And O 2 Matricesmentioning

confidence: 90%

See 1 more Smart Citation

Matrix isolation studies of 185nm light-induced cage reactions of o-chlorobenzaldehyde

Tanaka

Fujiwara

Ogawa

et al. 2012

Journal of Molecular Structure

View full text Add to dashboard Cite

VUV light photolysis of o-chlorobenzaldehyde (CBA) has been investigated by infrared spectroscopy in cryogenic Ar and O 2 matrices. Previously reported photoinduced rotational isomerization from anti-to syn-CBA was confirmed in the Ar matrix. In addition, absorption bands associated with photoinduced rearrangement to benzoyl chloride were observed accompanying the weak bands due to the CO photolysis product. However, in the reactive O 2 matrix, isomerization was observed and there was no evidence of benzoyl chloride formation. A kinetic analysis revealed that rearrangement was a minor process under the present excitation energy. The TD-B3LYP calculations show that as the excitation energy increases the predissociation channel will open and the repulsive 1 (, * C-Cl ) and 1 (n, * C-Cl ) states are directly achievable by the 185 nm excitation. Photoinduced rearrangement will be caused by the reaction of thus dissociated cage pairs.

show abstract

“…In the infrared spectrum obtained after deposition, strong bands were observed at 1710 and 1705 cm −1 , which can be assigned to C=O stretching vibration of anti-CBA [10]. Fig.…”

Section: Photolysis Of Cba In the Ar And O 2 Matricesmentioning

confidence: 90%

“…o-chlorobenzaldehyde (CBA) in an Ar matrix [10]. Upon irradiation ( > 300 nm) the isomerization from anti-to syn-CBA was the dominant process.…”

Section: Akai Et Al Reported the Photoinduced Rotational Isomerizatimentioning

confidence: 99%

Matrix isolation studies of 185nm light-induced cage reactions of o-chlorobenzaldehyde

Tanaka

Fujiwara

Ogawa

et al. 2012

Journal of Molecular Structure

View full text Add to dashboard Cite

show abstract

“…The trans and the cis conformers are defined by the position of the carbonyl oxygen. The population ratio of the isomers of 2-chlorobenzaldehyde was investigated by NMR, 20 resulting in that only the O-trans isomer exists at room temperature. In the liquid state at room temperature, the trans form of the OCBZ is known to exist as a stable conformer.…”

Section: Optimized Geometries Of the Neat And Binary Mixturesmentioning

confidence: 99%

Theoretical and vibrational spectroscopic studies on binary mixture of o‐chlorobenzaldehyde

Fathima

Ramakrishnan

2008

J Raman Spectroscopy

View full text Add to dashboard Cite

In this work, a combined theoretical and spectroscopic study of binary mixture of liquid ochlorobenzaldehyde (OCBZ) is reported using ab initio calculations, Raman and infrared (IR) spectroscopies. The purpose of this study was twofold: firstly, to describe the interaction of OCBZ in terms of bonding energies and preferred geometries; secondly, to characterize the spectroscopic effects on the vibrational modes of OCBZ in the binary mixture of different polar and nonpolar solvents. Ab initio calculations have proven to be a valuable tool for predicting relevant molecular structure and molecular parameters in the intermolecular interactions.

show abstract

“…Rotational isomerisation of 2-chlorobenzaldehyde in rare gas matrices has been investigated by vibrational and electronic spectroscopies together with DFT calculations. 107 Upon UV irradiation the less-stable O-cis isomer is formed from the more stable O-trans isomer. The temperature dependence of the intensities of IR bands of the two isomers allows an enthalpy difference of 9.7AE0.2 kJ mol À1 between the two isomers to be calculated.…”

Section: Organic Compounds Containing a Group 17 Atommentioning

confidence: 99%

“…368 Organic compounds containing a group 17 atom Rotational isomerism of 2-chlorobenzaldehyde in low temperature rare gas matrices has been studied. 107 The more stable O-trans isomer is converted to the less stable Ocis isomer upon irradiation. The enthalpy difference between the two forms is estimated to be approximately 9.7 kJ mol À1 .…”

mentioning

confidence: 99%

Chemistry in low-temperature matrices

Almond

Goldberg

2007

Annu. Rep. Prog. Chem., Sect. C: Phys. Chem.

View full text Add to dashboard Cite

the Progress of Chemistry, Section C. The report is divided into sections: weak adducts and conformational isomers; reactions of atoms; high-temperature molecules; photochemistry; biological molecules; astrochemistry. The last two sections reflect the fact that matrix isolation now extends into areas outside the traditional mainstream disciplines of chemistry. There are a number of areas where substantial progress has been made during the period of this report. First, the routine use of laser-ablation to generate atoms and to initiate atomic reactions in matrices has increased the scope of matrix isolation to synthesise many new molecular species in inorganic chemistry. Laser-ablation allows ground state atoms to be more easily studied than is the case when atoms are produced by thermal methods. Moreover, this procedure allows atoms to be generated from materials where thermal production is difficult. Secondly, the manufacture of more efficient closed-cycle helium refrigerators allows hydrogen matrices to be deposited readily. A significant body of work therefore has focussed upon metal hydrides, dihydrogen complexes and other hydrogen species in matrices. Underpinning all of this experimental work are theoretical calculations, without which the correct identification of most matrix isolation molecules would remain dangerously ambiguous. Infrared spectroscopy remains-as it has for the past 50 years-the workhorse of matrix isolation studies. It does seem that this situation will not change-it is impossible to conceive of another spectroscopic method that combines the necessary sensitivity to study molecules at very low dilution with the structural information required to make a reasonably certain identification.

show abstract

Photoinduced rotational isomerization mechanism of 2-chlorobenzaldehyde in low-temperature rare-gas matrices by vibrational and electronic spectroscopies

Cited by 22 publications

References 23 publications

Matrix isolation studies of 185nm light-induced cage reactions of o-chlorobenzaldehyde

Matrix isolation studies of 185nm light-induced cage reactions of o-chlorobenzaldehyde

Theoretical and vibrational spectroscopic studies on binary mixture of o‐chlorobenzaldehyde

Chemistry in low-temperature matrices

Contact Info

Product

Resources

About