Kenji Sakota

Excited-State Triple-Proton Transfer in 7-Azaindole(H2O)2 and Reaction Path Studied by Electronic Spectroscopy in the Gas Phase and Quantum Chemical Calculations†

We have investigated the excited-state multiple-proton/hydrogen atom transfer reactions in the 7-azaindole water clusters, [7AI](H(2)O)(n) (n = 2,3), in the gas phase by combining electronic spectroscopy and quantum chemical calculations. The fluorescence excitation (FE) spectrum of 7AI(H(2)O)(2) has been observed by monitoring visible emission. In contrast, no vibronic bands are detected in the FE spectrum of 7AI(H(2)O)(3) when the visible emission is monitored. The dispersed fluorescence spectra of 7AI(H(2)O)(n) (n = 2,3) have been measured. The excitation of +180 cm(-1) band from the electronic origin of 7AI(H(2)O)(2) enhances the visible emission as compared with the 0-0 excitation. The +180 cm(-1) band is assgined to an intermolecular mode (σ(1)) of the cyclic hydrogen-bonded ring structure. The calculated S(1)-S(0) absorption spectrum for the cyclic hydrogen-bonded structure is in agreement with the FE spectrum around the 0-0 region. The excitation of σ(1) significantly promotes the reaction and generates the tautomeric form of 7AI(H(2)O)(2). These experimental results on 7AI(H(2)O)(n) (n = 2,3) are very similar to those on 7AI(CH(3)OH)(n) (n = 2,3) and 7AI(C(2)H(5)OH)(n) (n = 2,3). We conclude that the excited-state triple proton/hydrogen atom transfer (ESTPT/HT) occurs in 7AI(H(2)O)(2). Cuts of the potential energy surfaces along the proton/hydrogen atom transfer coordinates of 7AI(H(2)O)(n) (n = 2,3) and 7AI(CH(3)OH)(n) (n = 2,3) are comparatively calculated by quantum chemistry calculations (RI-CC2/cc-pVDZ and TD-DFT(B3LYP)/cc-pVDZ) to explore the mechanism of the ESTPT/HT reaction. The calculated results suggest that concerted proton transfers occur in 7AI(H(2)O)(2) as well as in 7AI(CH(3)OH)(2), whereas the potential barrier for the excited-state quadruple proton transfer in 7AI(H(2)O)(3) and 7AI(CH(3)OH)(3) is higher than those for ESTPT. The theoretical results are consistent with the observation of ESTPT/HT in 7AI(H(2)O)(2).

Cooperativity of hydrogen-bonded networks in 7-azaindole(CH3OH)n (n=2,3) clusters evidenced by IR-UV ion-dip spectroscopy and natural bond orbital analysis

IR-UV ion-dip spectra of the 7-azaindole (7AI)(CH(3)OH)(n) (n=1-3) clusters have been measured in the hydrogen-bonded NH and OH stretching regions to investigate the stable structures of 7AI(CH(3)OH)(n) (n=1-3) in the S(0) state and the cooperativity of the H-bonding interactions in the H-bonded networks. The comparison of the IR-UV ion-dip spectra with IR spectra obtained by quantum chemistry calculations shows that 7AI(CH(3)OH)(n) (n=1-3) have cyclic H-bonded structures, where the NH group and the heteroaromatic N atom of 7AI act as the proton donor and proton acceptor, respectively. The H-bonded OH stretch fundamental of 7AI(CH(3)OH)(2) is remarkably redshifted from the corresponding fundamental of (CH(3)OH)(2) by 286 cm(-1), which is an experimental manifestation of the cooperativity in H-bonding interaction. Similarly, two localized OH fundamentals of 7AI(CH(3)OH)(3) also exhibit large redshifts. The cooperativity of 7AI(CH(3)OH)(n) (n=2,3) is successfully explained by the donor-acceptor electron delocalization interactions between the lone-pair orbital in the proton acceptor and the antibonding orbital in the proton donor in natural bond orbital (NBO) analyses.

Photoionization-induced water migration in the amide group of trans-acetanilide-(H2O)1 in the gas phase.

IR-dip spectra of trans-acetanilide-water 1:1 cluster, AA-(H(2)O)(1), have been measured for the S(0) and D(0) state in the gas phase. Two structural isomers, where a water molecule binds to the NH group or the CO group of AA, AA(NH)-(H(2)O)(1) and AA(CO)-(H(2)O)(1), are identified in the S(0) state. One-color resonance-enhanced two-photon ionization, (1 + 1) RE2PI, of AA(NH)-(H(2)O)(1) via the S(1)-S(0) origin generates [AA(NH)-(H(2)O)(1)](+) in the D(0) state, however, photoionization of [AA(CO)-(H(2)O)(1)] does not produce [AA(CO)-(H(2)O)(1)](+), leading to [AA(NH)-(H(2)O)(1)](+). This observation explicitly indicates that the water molecule in [AA-(H(2)O)(1)](+) migrates from the CO group to the NH group in the D(0) state. The reorganization of the charge distribution from the neutral to the D(0) state of AA induces the repulsive force between the water molecule and the CO group of AA(+), which is the trigger of the water migration in [AA-(H(2)O)(1)](+).

Photoionization-Induced Water Migration in the Hydrated trans-Formanilide Cluster Cation Revealed by Gas-Phase Spectroscopy and Ab Initio Molecular Dynamics Simulation

Photoionization-induced water migration in the trans-formanilide-water 1:1 cluster, FA-(H(2)O)(1), has been investigated by using IR-dip spectroscopy, quantum chemical calculations, and ab initio molecular dynamics simulations. In the S(0) state, FA-(H(2)O)(1) has two structural isomers, FA(NH)-(H(2)O)(1) and FA(CO)-(H(2)O)(1), where a water molecule is hydrogen-bonded (H-bonded) to the NH group and the CO group, respectively. In addition, the S(1)-S(0) origin transition of FA(CO)-(H(2)O)(2), where a water dimer is H-bonded to the CO group, was observed only in the [FA-(H(2)O)(1)](+) mass channel, indicating that one of the water molecules evaporates completely in the D(0) state. These results are consistent with a previous report [Robertson, E. G. Chem. Phys. Lett., 2000, 325, 299]. In the D(0) state, however, [FA-(H(2)O)(1)](+) produced by photoionization via the S(1)-S(0) origin transitions of FA(NH)-(H(2)O)(1) and FA(CO)-(H(2)O)(1) shows essentially the same IR spectra. Compared with the theoretical calculations, [FA-(H(2)O)(1)](+) can be assigned to [FA(NH)-(H(2)O)(1)](+). This means that the water molecule in [FA-(H(2)O)(1)](+) migrates from the CO group to the NH group when [FA-(H(2)O)(1)](+) is produced by photoionization of FA(CO)-(H(2)O)(1). [FA-(H(2)O)(1)](+) produced by photoionization of FA(CO)-(H(2)O)(2) also shows the IR spectrum corresponding to [FA(NH)-(H(2)O)(1)](+). In this case, the water migration from the CO group to the NH group occurs with the evaporation of a water molecule. Ab initio molecular dynamics simulations revealed the water migration pathway in [FA-(H(2)O)(1)](+). The calculations of classical electrostatic interactions show that charge-dipole interaction between FA(+) and H(2)O induces an initial structural change in [FA-(H(2)O)(1)](+). An exchange repulsion between the lone pairs of the CO group and H(2)O in [FA-(H(2)O)(1)](+) also affects the initial direction of the water migration. These two factors play important roles in determining the initial water migration pathway.

Excited-state double-proton transfer dynamics of deuterated 7-azaindole dimers in a free jet studied by hole-burning spectroscopy

Fluorescence excitation and hole-burning spectra have been measured for deuterated 7–azaindole dimers [(7AI)2] in a free jet in order to investigate their excited-state double-proton transfer (ESDPT) dynamics. Only one transition system is observed in the S1–S0 region of the excitation spectrum of (7AI)2-dd, where two hydrogen atoms of the NH groups are deuterated. Two transition systems are observed in the spectrum of (7AI)2-hd in which one of the hydrogen atom of the NH groups is deuterated. The two systems have been ascribed to the S1–S0 transitions of (7AI)2-h*d and (7AI)2-hd*. In these molecules one monomer moiety, 7AI-h or 7AI-d, is excited in the S1 state. The separation of the two electronic origins has been determined to be 21 cm−1. In contrast to (7AI)2-hd, two monomer moieties must be simultaneously excited in the S1(1Bu) states of (7AI)2-dd and (7AI)2-hh. These findings can be consistently explained by considering that (7AI)2-dd and (7AI)2-hh in the S1 state have C2h symmetry, whereas (7AI)2-h*d and (7AI)2-hd* have Cs symmetry. The bandwidth for one quantum of the intermolecular stretching vibration of (7AI)2–h*d (4.1 cm−1) in the excitation spectrum is greater than 2.4 cm−1 for the stretching vibration of (7AI)2-hd*, indicating that the rate of the ESDPT reaction depends significantly on the excited site. These results support a concerted mechanism for proton transfer in (7AI)2-dd and (7AI)2-hh. We will discuss the reason for the observation of bi-exponential decays detected by photo-excitation of vibronic bands of (7AI)2 in a molecular beam with a femtoseond laser (A. Douhal, S. K. Kim and A. H. Zewail, Nature, 1995, 378, 260) on the basis of the symmetry of the 7AI dimers and vibrational mode-specific proton transfer.

IR-dip and IR-UV hole-burning spectra of jet-cooled 4-aminobenzonitrile-(H2O)1. Observation of π-type and σ-type hydrogen-bonded conformers in the CN site

Abstract The IR-dip spectra and IR–UV hole-burning spectra of jet-cooled 4-aminobenzonitrile–water 1:1 complex have been measured to investigate the effects of the introduction of two substituents into the aromatic ring on the hydrogen-bonding interaction and stable structures of the complex. We have obtained a clear evidence for the observation of three structural isomers by comparing the experimental IR spectra with the theoretical ones. The water molecule is bonded to the NH 2 site in isomer I, where the amino group can act as a proton donor and the amino hydrogen is bonded to the oxygen atom of water. Water is bonded to the CN site in isomers II and III. The structure of isomer II is very similar to benzonitrile–(H 2 O) 1 , where the water hydrogen is bonded to the cyano nitrogen and the oxygen atom of water is bonded to the ortho hydrogen atom. The water hydrogen is linearly hydrogen-bonded to the cyano nitrogen in isomer III. The intermolecular hydrogen bond in isomer II is σ-type, whereas that in isomer III is π-type. The proton-donor conformer in the NH 2 site and the σ-type linear conformer in the CN site have not been observed in the aniline–(H 2 O) 1 and benzonitrile–(H 2 O) 1 complexes, respectively. The observation of three stable structures has been successfully explained by atomic charges on the constituent atoms obtained by natural population analysis.

Spectroscopic study on the structural isomers of 7-azaindole(ethanol)(n) (n=1-3) and multiple-proton transfer reactions in the gas phase.

The resonance-enhanced two-photon ionization (RE2PI) and laser-induced fluorescence excitation spectra were recorded for the S(1)-S(0)(pipi( *)) region of the 7-azaindole(ethanol)(n) (n=1-3) [7AI(EtOH)(n) (n=1-3)] clusters in the gas phase to investigate the geometrical structures and the multiple-proton/hydrogen atom transfer reaction dynamics. Four and two structural isomers were identified for 7AI(EtOH)(2) and 7AI(EtOH)(3), respectively. Density functional theory calculations at the B3LYP/6-31++G( * *)/6-31G( *) level predicted four different conformations of the ethyl group for 7AI(EtOH)(2), in good agreement with the observation of the four structural isomers in the RE2PI spectra. Visible fluorescence from the tautomeric forms was observed in the S(1) states for all isomers of 7AI(EtOH)(2), but no sign of double-proton/hydrogen atom transfer and quadruple-proton/hydrogen atom transfer has been obtained in the electronic spectra of 7AI(EtOH)(1) and 7AI(EtOH)(3), respectively. These results suggest that the multiple-proton transfer reaction is cluster-size selective, and the triple-proton/hydrogen atom transfer potential is dominated by the cyclic hydrogen-bonded network in 7AI(EtOH)(2). The excitation of the in-phase intermolecular stretching vibration prominently enhances the excited-state triple-proton/hydrogen atom transfer reaction.

Electronic and infrared spectra of jet-cooled 4-aminobenzonitrile-H2O. Change of NH2 from proton acceptor to proton donor by CN substitution

Abstract The electronic and infrared spectra of jet-cooled 4-aminobenzonitrile–(H2O)1 (4ABN–(H2O)1) hydrogen-bonded complex have been measured by the resonance-enhanced multiphoton ionization (REMPI) and infrared-dip (IR-dip) spectroscopy. Both the amino and cyano groups form intermolecular hydrogen bond with water, providing two stable isomers. It has been found that the substitution of the CN group at the para-position of aniline changes the electronic nature of the amino group in the S0 state from a proton acceptor to a proton donor.

Weak hydrogen bonding motifs of ethylamino neurotransmitter radical cations in a hydrophobic environment: infrared spectra of tryptamine(+)-(N2)n clusters (n ≤ 6).

Size-selected clusters of the tryptamine cation with N2 ligands, TRA(+)-(N2)n with n = 1-6, are investigated by infrared photodissociation (IRPD) spectroscopy in the hydride stretch range and quantum chemical calculations at the ωB97X-D/cc-pVTZ level to characterize the microsolvation of this prototypical aromatic ethylamino neurotransmitter radical cation in a nonpolar solvent. Two types of structural isomers exhibiting different interaction motifs are identified for the TRA(+)-N2 dimer, namely the TRA(+)-N2(H) global minimum, in which N2 forms a linear hydrogen bond (H-bond) to the indolic NH group, and the less stable TRA(+)-N2(π) local minima, in which N2 binds to the aromatic π electron system of the indolic pyrrole ring. The IRPD spectrum of TRA(+)-(N2)2 is consistent with contributions from two structural H-bound isomers with similar calculated stabilization energies. The first isomer, denoted as TRA(+)-(N2)2(2H), exhibits an asymmetric bifurcated planar H-bonding motif, in which both N2 ligands are attached to the indolic NH group in the aromatic plane via H-bonding and charge-quadrupole interactions. The second isomer, denoted as TRA(+)-(N2)2(H/π), has a single and nearly linear H-bond of the first N2 ligand to the indolic NH group, whereas the second ligand is π-bonded to the pyrrole ring. The natural bond orbital analysis of TRA(+)-(N2)2 reveals that the total stability of these types of clusters is not only controlled by the local H-bond strengths between the indolic NH group and the N2 ligands but also by a subtle balance between various contributing intermolecular interactions, including local H-bonds, charge-quadrupole and induction interactions, dispersion, and exchange repulsion. The systematic spectral shifts as a function of cluster size suggest that the larger TRA(+)-(N2)n clusters with n = 3-6 are composed of the strongly bound TRA(+)-(N2)2(2H) core ion to which further N2 ligands are weakly attached to either the π electron system or the indolic NH proton by stacking and charge-quadrupole forces.

IR spectroscopy of monohydrated tryptamine cation: Rearrangement of the intermolecular hydrogen bond induced by photoionization

Rearrangement of intermolecular hydrogen bond in a monohydrated tryptamine cation, [TRA(H(2)O)(1)](+), has been investigated in the gas phase by IR spectroscopy and quantum chemical calculations. In the S(0) state of TRA(H(2)O)(1), a water molecule is hydrogen-bonded to the N atom of the amino group of a flexible ethylamine side chain [T. S. Zwier, J. Phys. Chem. A 105, 8827 (2001)]. A remarkable change in the hydrogen-bonding motif of [TRA(H(2)O)](+) occurs upon photoionization. In the D(0) state of [TRA(H(2)O)(1)](+), the water molecule is hydrogen-bonded to the NH group of the indole ring of TRA(+), indicating that the water molecule transfers from the amino group to NH group. Quantum chemical calculations are performed to investigate the pathway of the water transfer. Two potential energy barriers emerge in [TRA(H(2)O)(1)](+) along the intrinsic reaction coordinate of the water transfer. The water transfer event observed in [TRA(H(2)O)(1)](+) is not an elementary but a complex process.