• 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.

• Bulletin of the Korean Chemical Society
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• v.15 no.7
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• pp.571-576
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• 1994

The photoreactions of $ReH_5(Cyttp)\;(1)\;(Cyttp=PhP(CH_2CH_2CH_2PCy_2)_2)\;with\;CO,\;CO_2\;and\;PMe_3 has been investigated to find the differences in reactivities from those of trismonophosphine analog. Irradiation of 1 under CO, $CO_2$ and excess $PMe_3$ in benzene results in the formation of the complexes, $ReH(CO)_2(Cyttp)\;(2),\;ReH_2({\eta}^2-HCO_2)(Cyttp)\;(3)\;and\;$ReH_3(PMe_3)(Cyttp)$ (4), respectively. The resulting products suggest that photoreactions of $ReH_5(Cyttp)$ proceed by photoextrusion of $H_2$ giving a phototransient species "$ReH_3$(Cyttp)" which can be trapped by CO, $CO_2\;and\;PMe_3$. The structures of 2, 3 and 4 are inferred based on $^1H,\;^{31}P$ NMR and I. R spectroscopy.

• Bulletin of the Korean Chemical Society
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• v.19 no.3
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• pp.308-313
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• 1998

A thermally irreversible photochromic system, 2,3-bis(2,4,5-trimethyl-3-thienyl)maleic anhydride (MTMA), has been studied by semi-empirical molecular orbital methods. There are one pair of stable conformations for the closed-ring form and three pairs for the open-ring form, each pair consisting of two mirror-image conformations. Interconversion between the parallel and anti-parallel conformations of the open-ring form is restricted due to high energy barriers. Only the anti-parallel conformation appears to be responsible for photochromic cyclization. Thermostability of the compound is attributed to an avoided crossing at high energy in the ground states of the isomers, whereas the photoreactivity can be explained by the mutually connected excited singlet (S1) states of the isomers, forming a double well potential with a low energy barrier. The large solvent effects can be partly explained with the low dipole moment of the anti-parallel conformation of MTMA in the S1 state. The large variation of quantum efficiency suggests that excess vibronic energy can be utilized to provide the activation energy for the photochromic reaction.

• Analytical Science and Technology
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• v.19 no.6
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• pp.504-511
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• 2006

Polysilanes with organic substituents such as methyl and phenyl were synthesized by Wurtz dechlorination-condensation reactions using ultrasonic from organochlorosilanes. The yields were compared with the results of thermal dechlorination-condensation reactions. Properties such as thermogravimetric analysis and photoreactivity were investigated for the possibility of applications.

• 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 the Korean Chemical Society
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• v.56 no.4
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• pp.484-490
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• 2012

The tin (IV) oxide nanoparticles are prepared by controlled precipitation method and calcined at temperatures of $200-600^{\circ}C$. The prepared $SnO_2$ nanoparticles characterized by XRD patterns, TEM image, IR and UV-Vis spectra. The XRD patterns and TEM image show the tetragonal structure and spherical morphology for $SnO_2$ nanoparticles, respectively. The photocatalytic activity of the prepared $SnO_2$ nanoparticles studied in degradation reaction of methylene blue (MB). The results show the size of nanoparticles, band-gap energy and photocatalytic activity of $SnO_2$ depends on the calcinations temperature. The $SnO_2$ nanoparticles calcined at $500^{\circ}C$ indicated the highest photoreactivity. Also, the zero-valent tin (ZVT) nanoparticles with tetragonal structure are prepared by a reducing agent and used as a catalyst in degradation of MB. In basic pH of 11, the degradation >95% of MB at time 150 min obtained at presence of ZVT nanoparticles.

• Macromolecular Research
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• v.16 no.1
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• pp.31-35
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• 2008

Photoreactive polymers as a color filter resist containing both photoreactive acrylate and cinnamate double bonds were synthesized usin two step reactions. The chemical structures of the synthesized polymers were confirmed by $^1H$-NMR and FT-IR spectroscopy. The photoreactive polymers were quite soluble in most common organic solvents and produced excellent quality thin films by spin-coating. The photocuring kinetics of the acrylate and cinnamate double bonds were examined by FT-IR and UV- Vis spectroscopy, which confirmed the excellent photoreactivity of both the acrylate and cinnamate double bonds in the polymers. Upon UV irradiation, photocuring was almost completed within approximately 5 min, irrespective of the type of the prepolymers. The polymers also exhibited superior thermal stability, showing little change in transmittance in the visible region even after heating to $250^{\circ}C$ for one hour. Photolithographic micropatterns could be obtained with a resolution of a few microns.

• Journal of the Korean Chemical Society
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• v.21 no.6
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• pp.434-439
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• 1977

The electronic structures of 4-pyridone and lutidone are studied by the SCF MO-CI PPP method and by the configuration analysis method. The spectral data are consistent with the values calculated by the method. The polarization of $S_1({\pi},{\pi}^*)$ state is along the long molecular axis in both compounds. The lowest $({\pi},{\pi}^*)$1 state shows significant charge transfer (16∼18%) from ${\pi}$ bonding orbital of C=O moiety to ${\pi}^*$ antibonding orbital of divinyl amine moiety. The lowest triplet state shows much larger charge transfer (24∼29 %) but in opposite direction compared to that of $S_1({\pi},{\pi}^*)$ state.

• Journal of the Mineralogical Society of Korea
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• v.23 no.2
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• pp.161-170
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• 2010

Many microbes, including both bacteria and fungi, produce manganese (Mn) oxides by oxidizing soluble Mn(II) to form insoluble Mn(IV) oxide minerals, a kinetically much faster process than abiotic oxidation. These biogenic Mn oxides drive the Mn cycle, coupling it with diverse biogeochemical cycles and determining the bioavailability of environmental contaminants, mainly through strong adsorption and redox reactions. This mini review introduces recent findings based on quantum mechanical density functional theory that reveal the detailed mechanisms of toxic metal adsorption at Mn oxide surfaces and the remarkable role of Mn vacancies in the photochemistry of these minerals.

• Journal of the Korean Chemical Society
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• v.54 no.1
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• pp.13-22
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• 2010

The photophysical properties of 7-diethylaminocoumarin (DEAC) laser dye have been measured in different solvents. The emission spectrum of DEAC has also been measured in cationic (CTAC) and anionic (SDS) micelles. The laser parameters have been calculated in different solvents namely acetone, dioxane, ethanol and dimethylforamide(DMF). The photoreactivity of DEAC has been studied in $CCl_4$ solvent using 366 nm light. The values of photochemical yield (${\Phi}_c$) and rate constant (k) are determined. The interaction of organic acceptors such as picric acid (PA), tetracyanoethylene (TCNE) and 7,7,8,8-tetracynoquinonedimethane (TCNQ) with DEAC are also studied using fluorescence measurements in acetonitrile ($CH_3CN$). The electrochemical investigation of (DEAC) has been carried out using cyclic voltammetry and convolutive voltammetry combined with digital simulation technique at a platinum electrode in 0.1 mol $L^{-1}$ tetrabutyl ammonium perchlorate (TBAP) in $CH_3CN$ solvent. The electrochemical parameters of the investigated compound were determined using cyclic and convolutive voltammetry. The extracted electrochemical parameters were verified and confirmed via digital simulation method.