• Journal of the Korean Chemical Society
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• v.67 no.6
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• pp.407-414
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• 2023

The present study uses quasi-classical trajectory procedures to examine the vibrational relaxation and dissociation of the methyl and ring C-H bonds in excited methylpyrazine (MP) during collision with either N₂ or O₂. The energy-loss (-ΔE) of the excited MP is calculated as the total vibrational energy (E_T) of MP is increased in the range of 5,000 to 40,000cm^-1. The results indicate that the collision-induced vibrational relaxation of MP is not large, increasing gradually with increasing E_T between 5,000 and 30,000 cm^-1, but then decreasing with the further increase in E_T. In both N₂ and O₂ collisions, the vibrational relaxation of MP occurs mainly via the vibration-to-translation (V→T) and vibration-to-vibration (V→V) energy transfer pathways, while the vibration-to-rotation (V→R) energy transfer pathway is negligible. In both collision systems, the V→T transfer shows a similar pattern and amount of energy loss in the ET range of 5,000 to 40,000cm^-1, whereas the pattern and amount of energy transfer via the V→V pathway differs significantly between two collision systems. The collision-induced dissociation of the C-H_methyl or C-H_ring bond occurs when highly excited MP (65,000-72,000 cm^-1) interacts with the ground-state N₂ or O₂. Here, the dissociation probability is low (10^-4-10^-1), but increases exponentially with increasing vibrational excitation. This can be interpreted as the intermolecular interaction below E_T = 71,000 cm^-1. By contrast, the bond dissociation above E_T = 71,000 cm^-1 is due to the intramolecular energy flow between the excited C-H bonds. The probability of C-H_methyl dissociation is higher than that of C-H_ring dissociation.

• Bulletin of the Korean Chemical Society
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• v.16 no.10
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• pp.972-976
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• 1995

A trace amount of 4-biphenylcarboxylate having a pre-twisted biphenyl moiety was attached to a poly(methyl methacrylate) side chain and the fluorescence properties of the chromophore were investigated in various solvents such as ethyl acetate and butyl chloride. At room temperature, the polymer exhibited a distinct red shift of the short wavelength emission (325 nm) and an enhanced emission intensity around 430 nm upon excitation at the absorption red edge. The temperature dependence of the intensity ratio (R) of the 325 nm emission to the 430 nm emission was observed when exciting at the red edge over the temperature range between -20 and 60 ℃. However, the temperature dependence was not observed when exciting at the shorter wavelength. The Arrhenius plot of the R value shows the activation energy of 6.0 kJ/mol which is in good agreement with the energy required for the twist of the biphenyl moiety. Together with the results of red edge excitation effects it was concluded that the pre-twisted geometry of the biphenyl moiety is preserved by the restriction of the polymer chain to facilitate the formation of the twisted intramolecular charge transfer (TICT) state upon excitation.

• Proceeding of EDISON Challenge
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• 2015.03a
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• pp.163-166
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• 2015

Intramolecular energy migration in a cyclic porphyrin array is spontaneous transfer of energy from one excited site to another. Since the efficiency of energy migration is inversely proportional to distance, the energy migration is occurred on their adjacent sites more often than distant ones. Therefore, the energy migration in the cyclic porphyrin array is largely dependent on their conformational characters. However, evaluation of conformational information by means of experimental tools is ambiguous since their limited resolution. In this work, we calculate the internal angle and distance distributions of cyclic porphyrin arrays using molecular dynamics simulations to obtain conformational information. To evaluate the angle and distance distributions respect to molecular size, we constructed molecules with n porphyrin dimers (n=1,3,7) in implicit solvent environment. Performing molecular dynamics simulations, we modulated alkyl groups to investigate additional conformational effects of the system.

• Journal of Photoscience
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• v.1 no.1
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• pp.53-59
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• 1994

Molecular orientation and polarity of solubilization site of dipolar azobenzenes solubilized in micellar solutions are discussed. The polarity of solubilization was estimated by using Taft $\pi$$^*$ scale with linear solvation energy relationship, $\Delta$E=$\Delta$E$_0$ + S($\pi$$^*$ + d$\delta$)+a$\alpha$ + b$\beta$. Hydrogen bonding effects were taken into account for the estimation of micropolarity. The polarity that azobenzenes experienced in the miceliar solutions was close to water which represented that the azobenzenes were mostly solubilized at the interface. For the orientations of azobenzenes were concerned, the nitro group of NPNOH faced the interface and the hydroxy group of NPNO$^-$ located at the interfacial area.

• Journal of Photoscience
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• v.9 no.1
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• pp.9-12
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• 2002

A porphyrin derivative covalently tinted to Ni aria-macrocycle complex has been prepared. Absorption spectrum of porphyrin-Ni aria-macrocycle dyad (λ$\^$max/$\sub$a/=227 nm) was observed to similar to a sum of those of tetratolylporphyrin (λ$\^$max/$\sub$a/=419 nm) and Ni aza-macrocycle (λ$\^$max/$\sub$a/=227 nm), indicating no electronic interaction between porphyrin and Ni aza-macrocycle moieties. Fluorescence quantum yield of dyad (${\Phi}$$\sub$f/= 0.10) was same to that of tetratolylporphyrin (${\Phi}$$\sub$f/= 0.10). Photoinduced intramolecular electron transfer or energy transfer from excited porphyrin moiety to Ni(II) aza-macrocycle moiety should be very inefficient in dyad.

• Bulletin of the Korean Chemical Society
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• v.7 no.5
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• pp.395-399
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• 1986

Intramolecular proton transfer equilibria of acetamide and methyl carbamate have been studied theoretically by MNDO MO method. For both substrates, carbonyl-O protonated tautomer was found to be the most stable form, the next most stable one being N-protonated form. Gas phase proton transfers take place by the 1,3-proton rearrangement process and in all cases have prohibitively high activation barriers. When however one solvate water molecule participates in the process, the barriers are lowered substantially and the process proceeds in an intermolecular manner through the intermediacy of the water molecule via a triple-well type potential energy surface; three wells correspond to reactant(RC), intermediate(IC) and product complex(PC) of proton donor-acceptor pairs whereas two transition states(TS) have proton-bridge structure. General scheme of the process can be represented for a substrate with two basic centers(heteroatoms) of A and B as, $$ABH\limits^+\;+\;H_2O\;{\to}\;ABH\limits^+{\cdots}{\limits_{RC}}OH_2\;{\to}\;AB{\cdots}H\limits_{TS}^+{\cdots}{\limits_{1}}OH_2\;{\to}\;AB{\cdots}{\limits_{IC}}H\limits^+OH_2\;{\to}\;BA{\cdots}H\limits_{TS}^+{\cdots}{\limits_{2}}OH_2\;{\to}\;BA H\limits^+{\cdots}{\limits_{PC}}OH_2\;{\to}\;BAH\limits^+\;+\;H_2O$$ Involvement of a second solvate water had negligible effect on the relative stabilities of the tautomers but lowered barrier heights by 5∼6 Kcal/mol. It was calculated that the abundance of the methoxy-O protonated tautomer of the methyl carbamate will be negligible, since the tautomer is unfavorable thermodynamically as well as kinetically. Fully optimized stationary points are reported.

• Journal of the Korean Chemical Society
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• v.34 no.6
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• pp.637-640
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• 1990

Bis (4,6-dichloropyrimidine-5-yl) alkanes as the frame of "intramolecular electronic energy transfer" system have been synthesized and the H-chelates of $\alpha$-(4-cyanomethylquinoline-6-chloropyrimidine-5-yl)-$\omega$-(4,6-dichloropyrimidine-5-yl) alkanes have been synthesized from bis (4,6-dichloropyrimidine-5-yl) alkanes and 2-cyanomethylquinoline. The structures of the compounds have been studied by spectral methods.

• Bulletin of the Korean Chemical Society
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• v.12 no.6
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• pp.678-681
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• 1991

The Wittig-oxy-Cope rearrangements of deprotonated diallyl ether, I, $CH_2={\bar{C}}H-CH-O-CH_2-CH=CH_2$, have been investigated theoretically by the AM1 method. A two step mechanism forming a Wittig product ion, II, $(CH_2=CH)$ $(CH_2=CH-CH_2)$ $CHO^-$, through a radical-pair intermediate was found to provide the most favored reaction pathway in the Wittig rearrangement. The subsequent oxy-Cope rearrangement from species II also involves a two step mechanism through a biradicaloid intermediate. The intramolecular proton transfer in I (to form $CH_2=CH-CH_2-O-{\bar{C}}H-CH=CH_2$) is a higher activation energy barrier process compared to the Wittig and oxy-Cope rearrangements and is considered to be insignificant. These results are in good agreement with the condensed-phase as well as gas-phase experimental results.

• Bulletin of the Korean Chemical Society
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• v.34 no.11
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• pp.3211-3217
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• 2013

Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations have been employed to investigate the molecular structures and absorption spectra of three D-${\pi}$-A-type organic dyes (C1-1, D5 and TH208) containing identical ${\pi}$-spacers and electron acceptors, but different aromatic amine electron-donating groups (tetrahydroquinoline, triphenylamine and phenothiazine). The coplanar geometries indicate that the strong conjugation is formed in the dyes. The electronic structures suggest that the intramolecular charge transfer from the donor to the acceptor occurs, and the electron-donating ability of tetrahydroquinoline is stronger than those of triphenylamine and phenothiazine. The computed orbital energy levels of these dyes confirm that the electrons could be injected from the excited dyes to the semiconductor conduction band and the oxidized dyes could be reduced effectively by electrolyte. The TD-DFT results show that the CAM-B3LYP/6-31+G(d, p) is suitable for calculating the absorption spectra. The first absorption band for these dyes is assigned to the HOMO${\rightarrow}$LUMO and HOMO-1${\rightarrow}$LUMO transitions.

• Bulletin of the Korean Chemical Society
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• v.26 no.1
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• pp.77-84
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• 2005

We prepared the new nonlinear optical chromophores that show fairly high microscopic nonlinearity through intramolecular charge transfer. Phenothiazine and carbazole units played an important role to contribute high electron donability and connect the resonance pathway via conjugative effect in the cyclized ring beside the aromatic ring. Theoretical calculation, electrochemical analysis, and absorption spectroscopic study gave us useful information about the energy states and microscopic nonlinearities of two serial chromophores. We compared the microscopic nonlinearities of four chromophores with the conjugation length and electron donability in the push-pull type NLO chromophores. The effect of gradient donability and lengthening the conjugation were investigated on the electronic state and microscopic nonlinearity.