• Bulletin of the Korean Chemical Society
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• v.13 no.6
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• pp.684-688
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• 1992

Three photocyclodimers of 5,7-dimethoxycoumarin (DMC) were isolated and characterized from the photolysis of DMC in acetonitrile. The configuration of the dimers was found to be anti head-to-head, syn head-to-head and syn head-to-tail, respectively. The number and the ratio of the products are solvent dependent. The anti head-to-head dimer is favored in nonpolar solvents and the preference decreases as the solvent polarity increases giving almost 100${\%}$ syn dimers and less than 1${\%}$ anti dimer from methanol solution. The overall yields of dimers also increase with the solvent polarity. From sensitization and quenching experiments, anti dimer was found to be formed via excited singlet state while syn dimers were formed via both excited singlet and triplet states.

• Journal of the Korean Vacuum Society
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• v.7 no.s1
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• pp.20-24
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• 1998

Photploymer films are widely used in printing and electronic industries, and their usage is expanding to encompass holography, data storage and data processing, optical waveguides and compact disks, etc. One of widely used photoplymerization initiator, 20chloro-hexaarylbiimidazole (o-Cl-HABI), is studied by laser flash photolysis in dichloromethane solution in the absence and presence of the visible light photosensitizing dye, 2, 5-bis[(2, 3, 6, 7 -tetrahydro- 1H, 5H -benzo [i, j,] quinolizin -1-yl) methylene]-cyclopenta-none, (JAW). In the presence of JAW, an increase in triarylimidazolyl radicals L.formation is observed in relative to the absence of JAW. The mechanism of this photosensitizing dissociation is concluded as the dissociation of the o-Cl-HABI radical anion formed by the electron transfer from excited singlet state of JAW to o-Cl-HABI. The observed formation of L.radicals exhibits a linear dependence on o-Cl-HABI concentration. The rate constant of electron transfer obtained from this dependence is equal to (1.0$\pm$0.2) x $10^9 M^{-1}s^{-1}$. No reaction between the excited triplet state of JAW and o-Cl-HABI is found.

• Bulletin of the Korean Chemical Society
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• v.7 no.4
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• pp.289-293
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• 1986

The photocycloaddition reactivity of 5,7-dimethoxycoumarin (DMC) to thymidine is much higher than that of cis-syn 8-methoxypsoralen $<\array{4^{\prime},5\\5^{\prime},6}>$ thymidine monoadducts, due to the steric effect. The different rate is also due to the relative reactivity of the singlet rather than the triplet excited state of the compounds. The biadducts of 8-methoxypsoralen and thymidine are first splitted into 4',5'-monoadducts and thymidine, not into 3,4'-monoadducts and thymidine by 254 nm light.

• Journal of Photoscience
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• v.10 no.1
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• pp.9-20
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• 2003

Recent studies on the photoreactivity of l,4-unsaturated systems have changed some ideas that were firmly established in this area of research for many years. Thus, we have described the first examples of 2-aza-di-$\pi$-methane (2-ADPM) rearrangements promoted by triplet-sensitization and by single electron transfer (SET) using electron-acceptor sensitizers. These reactions afford N-vinylaziridine and cyclopropylimine photoproducts in the first examples of di-$\pi$-methane processes that yield three-membered ring heterocycles. l-Aza-1,4-dienes also undergo SET-promoted l-aza-di-$\pi$-methane (l-ADPM) rearrangements via radical-cation intermediates using electron acceptor sensitizers. In some cases, alternative cyclizations yielding different carbocycles and heterocycles have been observed. The l-ADPM and di-$\pi$-methane (DPM) reactions also occur via radical-anion intermediates on irradiation using electron donor sensitizers. On the other hand, the photoreactivity reported for $\beta$,${\gamma}$-unsaturated aldehydes for many years was decarbonylation to the corresponding alkenes. However, our studies demonstrate that these compounds undergo the oxa-di-$\pi$-methane (ODPM) rearrangement with high chemical and quantum efficiency. A comparison of the photochemical reactivity of $\beta$,${\gamma}$-unsaturated aldehydes and corresponding methyl ketones has shown that the ketones do not undergo the ODPM rearrangement while the corresponding aldehydes are reactive by this pathway. Monosubstituted $\beta$,${\gamma}$-unsaturated aldehydes at C-2 undergo the ODPM rearrangement yielding the corresponding cyclopropane carbaldehydes diastereoselectively. Finally, we have described the first examples of reactions, similar to the well know Norrish Type I process, which take place in the triplet excited state of $\beta$,${\gamma}$-unsaturated carbonyl compounds by excitation of the C-C double bond instead of the carbonyl group.

• Journal of the Korean Chemical Society
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• v.29 no.4
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• pp.426-436
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• 1985

Preparative and kinetic photochemical reactions of several benzanilides were studied. Several substituted benzanilides were synthesized by acylation of substituted anilines with substituted benzoyl chlorides. While benzanilide gave a photo-Fries type reaction product, 2-chlorobenzaniline, 2-bromobenzanilide, and 2-methoxybenzanilide gave a photocyclization reaction product, phenanthridone. Since 8-chlorophenanthridone was obtained from 2,2'-dichlorobenzanilide, the carbonyl phenyl is the excited site. Quantum yield of photocyclization of 2-chlorobenzanilide, 2'-chlorobenzanilide, and 2-methoxybenzanilide were obtained. 2-Chlorobenzanilide was photocyclized effectively and 2'-chlorobenzanilide ineffectively. Since the oxygen present in the reaction medium retarded the photocyclization reaction of 2-chlorobenzanilide, the triplet state of 2-chlorobenzanilide is involved. The mechanism of the photocyclization of 2-chlorobenzanilide is suggested: $\pi-complex$ between carbonyl phenyl and N-phenyl was formed from the triplet state of 2-chlorobenzanilide; neighbour phenyl (N-phenyl) assists for leaving of chlorine from carbonyl phenyl to make an intermediate, cyclized conjugated radical, because electron donating group on the N-phenyl ring accelerated the reaction; hydrogen detachment from the intermediate is obviously not a rate determined step because there was no isotope effect on the rate of photocyclization. The photocyclization reaction rate of 2-methoxybenzanilide was faster in the presence of oxygen than in the absence of oxygen. Thus, the singlet excited state of 2-methoxybenzanilide is involved in the reaction. Probably, the intermediate, methoxyhydro-phenanthridone is oxidized by oxygen in the medium to give phenanthridone.

• Bulletin of the Korean Chemical Society
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• v.26 no.8
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• pp.1190-1196
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• 2005

Halopyrroles, N-substituted 2-halopyrroles were prepared by halogenation of N-substituted pyrroles with NBS, NCS, or surfuryl chloride. N-Substituted 3-halopyrroles were synthesized by acid-catalyzed thermal and photochemical isomerization reactions of N-substituted 2-halopyrroles. Both the thermal and photochemical reactions were acid-catalyzed. For the acid-catalyzed isomerization, a mechanism of [1,3] bromine shift followed by deprotonation is operated. For the acid-catalyzed photoisomerization, an excited triplet state of 2-protonated N-benzyl-2-halopyrrole produces an intermediate N-substituted pyrrole complex with halonium ion which is equilibrated with N-substituted pyrrole plus halonium ion, and then the halonium ion newly adds to 3-position of N-substituted pyrrole followed by deprotonation to afford N-benzyl-3-halopyrrole.

• Bulletin of the Korean Chemical Society
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• v.3 no.1
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• pp.30-33
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• 1982

Photochemical and thermal solvolysis of 2,3,4-picolyl chlorides (2,3,4-PC) were studied in amine solvents and the results were correlated with the electronic structures calculated by PPP-SCF-MO CI method. Activation parameters show that the thermal solvolysis of PC is $S_N2$ type rcaction. The rates of thermal reaction in pyridine or t-butylamine solvent decrease in the order of 2-PC > 3-PC > 4-PC. These results are consistent with the predictions based on the electron densities of picolyl chlorides. In photosolvolysis, the same products as those of thermal reactions were obtained. The results indicate that photochemical solvolysis undergoes through heterolytic cleavage. Relative quantum yields of photosolvolysis of 2,3,4-picolyl chlorides in t-butylamine solvent were determined to be 0.73, 1, and 0.50 respectively. These results are in good agreement with the electron densities of the excited triplet state of picolyl chlorides.

• Bulletin of the Korean Chemical Society
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• v.14 no.4
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• pp.506-510
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• 1993

Irradiation of 1,4-diphenylbutadiyne (DPB) with a mixture of electron-deficient and electron-rich olefins in deaerated tetrahydrofuran yields a 1 : 1 primary photoadduct between DPB and electron-deficient olefins. Irradiation of the primary photoadduct of DPB and dimethyl fumarate (DMFu) with various olefins such as DMFu, acrylonitrile (AN), and 2,3-dimethyl-2-butene (DMB) in deaerated tetrahydrofuran yields regiospecific 1 : 1 photoadducts. The electron-deficient olefins are more reactive than electron-rich olefins in the photoreaction which proceeds through excited triplet state.

• Proceeding of EDISON Challenge
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• 2014.03a
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• pp.251-262
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• 2014

최근 유기 발광 다이오드(Organic Light Emitting Diodes; OLED)가 각광받고 있어 이를 개발하기 위한 좀 더 효율적이고 실용적인 OLED 구조의 예측이 필요해지고 있다. 본 연구는 가장 기초적인 OLED dye의 형태인 $Ru(bpy){_3}^{2+}$와 그와 유사한 구조의 발광 물질이 전기화학발광(ECL) 현상을 통해 방출하는 빛의 특성을 계산하는 것을 목적으로 한다. EDISON 화학 서버의 GAMESS 프로그램을 사용하여 $Ru(bpy){_3}^{2+}$와 유도체들의 바닥상태(ground state)와 첫 번째 들뜬 상태(first excited state)를 계산하였다. Basis set으로는 MINI와 3-21G 혹은 SBKJC를 사용하였다. 들뜬 상태 계산은 configuration interaction with single excitation(CIS)을 이용하여 단일항(singlet)과 삼중항(triplet) 상태에서 바닥과 들뜬 상태의 최적 구조에 대한 계산을 수행하였다. 다양한 방법으로 방출 파장을 계산한 결과를 바탕으로 $Ru(bpy){_3}^{2+}$와 다양한 유도체들의 에너지 계산에 어떤 방법이 효율적으로 적용될 수 있을지 탐색하였다. 같은 계산방법들이 중심 금속이 이리듐(Ir)인 분자에도 적용이 될 수 있을지 알아보기 위해 $lr(mppy)_3$에도 적용하였다. 본 연구를 통하여 얻어진 방식은 시간을 절약하고 더 효율적인 $Ru(bpy){_3}^{2+}$ 유도체 계산에도 사용할 수 있을 것이다.

• Journal of the Korean Chemical Society
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• v.20 no.5
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• pp.398-405
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• 1976

A new compound, 1,2-bispyrazyl ethylene,is synthesized starting from pyrazine carboxylic acid and methyl pyrazine. The compound is characterized utilizing UV-VIS, IR, NMR and mass spectra along with elemental analysis. Spectroscopic properties are studied from UV-VIS and fluorescence spectra. From unusual salt effects on fluorescence spectra, it is believed that $(n,\;{\pi}^*)$ state has about the same energy as $({\pi},\;{\pi}^*)$ state. The compound fluoresces from $({\pi},\;{\pi}^*)$ state with the quantum yield of 0.025 at $77^{\circ}K$ compared to near unity for stilbene at the same temperature indicating the efficient intersystem crossing to triplet state, because of strong $(n,\;{\pi}^*)$ and $({\pi},\;{\pi}^*)$ mixing in the lowest excited state.