Electronic spectra of jet-cooled calix[4]arene and its van der Waals clusters: Encapsulation of a neutral atom in a molecular bowl

Ebata, Takayuki; Hodono, Yuki; Ito, Takafumi; Inokuchi, Yoshiya

doi:10.1063/1.2723068

Cited by 16 publications

(38 citation statements)

References 12 publications

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“…It can be seen that the calculated H-bonded OH stretching vibra- tional frequency in the ground state is 3181 cm −1 . The corresponding experimental datum is 3158 cm −1 [33].…”

Section: Methodsmentioning

confidence: 99%

“…Four intramolecular hydrogen bonds O-H· · · O are formed in the cone conformers of C4A, which allows C4A to act as host for a wide range of guests. Thus, C4A is an excellent model in which to study intramolecular hydrogen bonding in the excited state [32][33][34][35]. However, little information is available on electronic excited-state intramolecular hydrogen bonding due to the extremely short timescales involved.…”

Section: Introductionmentioning

confidence: 99%

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Role of intramolecular hydrogen bonding in the excited-state intramolecular double proton transfer (ESIDPT) of calix[4]arene: A TDDFT study

Wang

Hao

2016

Open Physics

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Abstract:The time-dependent density functional theory (TDDFT) method was performed to investigate the excitedstate intramolecular double proton transfer (ESIDPT) reaction of calix [4]arene (C4A) and the role of the intramolecular hydrogen bonds in the ESIDPT process. The geometries of C4A in the ground state and excited states (S 1 , S 2 and T 1 ) were optimized. Four intramolecular hydrogen bonds formed in the C4A are strengthened or weakened in the S 2 and T 1 states compared to those in the ground state. Interestingly, upon excitation to the S 1 state of C4A, two protons H1 and H2 transfer along the two intramolecular hydrogen bonds O1-H1· · · O2 and O2-H2· · · O3, while the other two protons do not transfer. The ESIDPT reaction breaks the primary symmetry of C4A in the ground state. The potential energy curves of proton transfer demonstrate that the ESIDPT process follows the stepwise mechanism but not the concerted mechanism. Findings indicate that intramolecular hydrogen bonding is critical to the ESIDPT reactions in intramolecular hydrogen-bonded systems.

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“…It can be seen that the calculated H-bonded OH stretching vibra- tional frequency in the ground state is 3181 cm −1 . The corresponding experimental datum is 3158 cm −1 [33].…”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Role of intramolecular hydrogen bonding in the excited-state intramolecular double proton transfer (ESIDPT) of calix[4]arene: A TDDFT study

Wang

Hao

2016

Open Physics

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“…Figure 13a shows the LIF spectrum of jet-cooled C4A. 61 In the LIF spectrum, the lowest frequency band at 35357 cm Õ1 is assigned to the band origin, since we do not observe any bands in the lower frequency region under expansion conditions with He carrier gas. In the higher frequency region of the band origin there are four bands up to 35500 cm…”

Section: õ1mentioning

confidence: 99%

“…19,20 Third, we show our recent laser spectroscopic study of jetcooled functional molecules, that is calixarene and crown ether. We report the structure of calix[4]areneÍX n (X = Ar and Ne) 61 and hydrated clusters of dibenzo-18-crown-6-ether (DB18C6), 62 by using double resonance spectroscopy. Finally, a time-resolved study of the vibrational energy relaxation (VER) of the OH stretching vibration, that is intramolecular and -cluster vibrational energy redistribution (IVR) and vibrational predissociation (VP) initiated by the IR excitation, of aromatic molecules and their clusters are described.…”

Section: í81mentioning

confidence: 99%

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Study on the Structure and Vibrational Dynamics of Functional Molecules and Molecular Clusters by Double Resonance Vibrational Spectroscopy

Ebata¹

2009

Bulletin of the Chemical Society of Japan

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Structure and dynamics of gas-phase molecules and their clusters formed in a supersonic jet has been a great interest to many researchers. Studies on these simple systems provide us with the fundamental concept of many physical and chemical phenomena observed in bulk systems. These studies are also important for the verification of theoretical prediction and quantum chemical calculations. Especially molecular clusters have been thought to be a good model for molecular level understanding of intermolecular interaction and relaxation in condensed phase. However, until the beginning of 1990, studies of molecular clusters mainly concentrated on electronic spectroscopy and very few studies were reported for vibrational spectroscopy. On the other hand, vibrational spectroscopy is essential in condensed phase, and there has been a gap between cluster science and condensed phase science. In 1993 we first reported infrared (IR)Í ultraviolet (UV) double resonance spectroscopy of the OH stretching vibration of phenol and its hydrated clusters in a supersonic jet. The observed vibrational spectra showed a characteristic feature of the H-bonding, that is a larger frequency shift as well as broadening of the OH stretching band, and the structures were unambiguously determined with the aid of quantum chemical calculation. It is not too much to say that the combination of double resonance vibrational spectroscopy and quantum chemical calculation has become a very popular method in cluster science. In this paper, we describe various double resonance vibrational spectroscopies in frequency domain. Typical examples of application are shown; determination of H-bonded clusters of benzonitrile, conformer selective vibrational spectroscopy for L-phenylalanine and its hydrated cluster, and study of the encapsulation structure of guest atom and molecules by functional molecules, calixarene and crown ether. Finally, time-domain studies for the dynamics of the vibrations are described. Picosecond IRÍUV pumpÍprobe spectroscopy is applied to study the vibrational energy relaxation (VER) of the OH stretching vibration of isolated aromatic molecules and the H-bonded clusters.

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Selective Probing of Potassium Ion in Solution by Intramolecular Excimer Fluorescence of Dibenzo‐Crown Ethers

et al. 2018

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Observation of an excimer fluorescence in solution is proposed for detecting the encapsulation of potassium ion as opposed to other alkali ions by dibenzo-crown ethers. The scheme has been validated by ultraviolet photodissociation (UVPD) spectroscopy of dibenzo-21-crown-7 and dibenzo-24-crown-8 complexes with potassium ion, K ⋅ DB21C7 and K ⋅ DB24C8, performed under cold (∼10 K) conditions in the gas phase and by quantum chemical calculations of the geometry and electronic structures of the complexes. Calculations suggest the formation of a closely spaced excimer structure of benzene rings only for the K ⋅ DB24C8. Interaction of the rings may lead to lifetime broadening in UV absorption, which is experimentally observed in the gas phase, indeed, only for this cold complex. Consistently, intramolecular excimer fluorescence of DB24C8 in solution is observed only for K ⋅ DB24C8. The excimer fluorescence is not observed with other alkali metal ions. The detection of such intramolecular excimer fluorescence can, therefore, potentially serve as a simple, background-free, selective probe of potassium ion in solution.

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Electronic spectra of jet-cooled calix[4]arene and its van der Waals clusters: Encapsulation of a neutral atom in a molecular bowl

Cited by 16 publications

References 12 publications

Role of intramolecular hydrogen bonding in the excited-state intramolecular double proton transfer (ESIDPT) of calix[4]arene: A TDDFT study

Role of intramolecular hydrogen bonding in the excited-state intramolecular double proton transfer (ESIDPT) of calix[4]arene: A TDDFT study

Study on the Structure and Vibrational Dynamics of Functional Molecules and Molecular Clusters by Double Resonance Vibrational Spectroscopy

Selective Probing of Potassium Ion in Solution by Intramolecular Excimer Fluorescence of Dibenzo‐Crown Ethers

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