• Journal of the Korean Chemical Society
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• v.31 no.2
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• pp.133-142
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• 1987

Stereoselectivities of (4+2) cycloaddition reactions of cyclopentadiene with the methyl-substituted allenic acids and esters were investigated by application of $\pi$-nonbonded interaction ($\pi$-NBI) theory. 2-FMO method has been found to be adequate for determination of endo selectivities of diene(LUMO)-dienophile (LUMO) interaction in the thermal reactions and diene (HOMO)-dienophile (LUMO) interaction in the Lewis acid catalyzed reactions. $\pi$-isoconjugate diene structure was formed by through-bond interaction of allene moiety with methyl group in the cumulated diene system; the methyl substituent acts as a conjugative chain and causes inter-level narrowing effect of the FMO's. In dienophiles which do not form $\pi$-isoconjugate diene system, methyl group acts merely as an electron donating group. In thermal reactions, the stereoselectivities are controlled by $\pi$-nonbonded secondary orbital interaction ($\pi$-NSOI) of methyl substituent, which behaves similarly as an ethylene molecule.

• Bulletin of the Korean Chemical Society
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• v.34 no.12
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• pp.3690-3694
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• 2013

The $H_2Ge=Ge:$ and its derivatives ($X_2Ge=Ge:$, X = H, Me, F, Cl, Br, Ph, Ar${\ldots}{\ldots}$) is a new species. Its cycloaddition reactions is a new area for the study of germylene chemistry. The mechanism of the cycloaddition reaction between singlet state Cl2Ge=Ge: and formaldehyde has been investigated with CCSD(T)//MP2/$6-31G^*$ method. From the potential energy profile, it could be predicted that the reaction has only one dominant reaction pathway. The reaction rule presented is that the two reactants first form a fourmembered Ge-heterocyclic ring germylene through the [2+2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge: atom in the four-membered Ge-heterocyclic ring germylene and the ${\pi}$ orbital of formaldehyde forming a ${\pi}{\rightarrow}p$ donor-acceptor bond, the four-membered Ge-heterocyclic ring germylene further combines with formaldehyde to form an intermediate. Because the Ge: atom in intermediate hybridizes to an $sp^3$ hybrid orbital after transition state, then, intermediate isomerizes to a spiro-Ge-heterocyclic ring compound via a transition state. The research result indicates the laws of cycloaddition reaction between $H_2Ge=Ge:$ and formaldehyde, and laid the theory foundation of the cycloaddition reaction between $H_2Ge=Ge:$ and its derivatives ($X_2Ge=Ge:$, X = H, Me, F, Cl, Br, Ph, Ar${\ldots}{\ldots}$) and asymmetric ${\pi}$-bonded compounds, which is significant for the synthesis of small-ring and spiro-Ge-heterocyclic compounds. The study extends research area and enriches the research content of germylene chemistry.

• Bulletin of the Korean Chemical Society
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• v.1 no.4
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• pp.123-126
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• 1980

Benzene solution of trans-1,2-bispyrazylethylene and electron deficient olefin, tetracyanoethylene, as a ${\pi}$-acceptor gave 1,2-bispyrazyl-3,3,4,4-tetracyanocyclobutane, a 2${\pi}$ + 2${\pi}$ cycloaddition product, on irradiation with 350 nm UV light. Fluorescence studies revealed the reaction to proceed through a singlet exciplex. The fluorescence of trans-1,2-bispyrazylethylene was quenched very efficiently by tetracyanoethylene with the quenching constant of 1.6 ${\times}$ 10$^{10}$M$^{-1}$s$^{-1}$ while electron rich olefin, tetramethylethylene, did not quench the fluorescence of bispyrazylethylene.

• Bulletin of the Korean Chemical Society
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• v.33 no.12
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• pp.4079-4083
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• 2012

The mechanism of the cycloaddition reaction between singlet state dichlorosilylene germylidene ($Cl_2Si=Ge:$) and acetone has been investigated with B3LYP/6-$31G^*$ and B3LYP/6-$31G^{**}$ method, from the potential energy profile, we predict that the reaction has one dominant reaction pathway. The presented rule of the reaction is that the two reactants firstly form a Si-heterocyclic four-membered ring germylene through the [2+2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge atom in the Si-heterocyclic four-membered ring germylene and the ${\pi}$ orbital of acetone forming a ${\pi}{\rightarrow}p$ donor-acceptor bond, the Si-heterocyclic four-membered ring germylene further combines with acetone to form an intermediate. Because the Ge atom in the intermediate hybridizes to an $sp^3$ hybrid orbital after the transition state, then, the intermediate isomerizes to spiro-heterocyclic ring compound involving Si and Ge (P4) via a transition state.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.02a
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• pp.372-372
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• 2010

We have investigated adsorption of selenophene on Si(100) at room temperature using high resolution photoemission spectroscopy (HRPES) and near edge X-ray absorption fine structure (NEXAFS) in the partial electron yield (PEY) mode. The Si 2p, C 1s, Se 3d spectra of selenophene on Si(100) show that selenophene is nondissociatively chemisorbed on Si(100)-$2{\times}1$ through [2+2] cycloaddition. NEXAFS has been conducted to characterize the adsorption geometry of selenophene on Si(100). Since the $\pi^*$ orbital of C=C bond show good angular dependence in carbon K-edge NEXAFS spectra, the angle $53{\pm}5^{\circ}$ determined from NEXAFS spectra. This majority structure is consistent with the [2+2] cycloaddition of selenophene to the dimer of the Si(100)-$2{\times}1$ surface.

• Macromolecular Research
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• v.15 no.2
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• pp.142-146
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• 2007

Poly[(1-(9-carbazoly1)ethylene)-co-(3-cinnamoyloxyoctyl-9-carbazolyl)] ethylene (PVK-Cin) was prepared by tethering cinnamate pendants to a carbazole group via an octylene spacer. The photopatternability of the new PVK based-polymer was investigated using a photocrosslinking reaction under UV light illumination $(\lambda=254nm)$. Blends of the PVK-Cin and a soluble poly(phenylene vinylene) (CzEh-PPV) were employed to study the photocrosslinking behavior. Well resolved lithographic patterns were observed in these polymer systems. PVK-Cin produced a blue light emitting pattern both before and after the photocrosslinking reaction. The blends of PVK-Cin and CzEh-PPV also showed corresponding emissions at 398 and 525 (560) nm in the film state.

• Polymer(Korea)
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• v.34 no.4
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• pp.313-320
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• 2010

New cinnamate group-containing copolymers for a self-curable, humidity-sensitive polyelectrolyte and polymeric anchoring agents were prepared by copolymerization of [2-[(methacryloyloxy) ethyl]dimethyl]propyl ammonium bromide(MEPAB), methyl methacrylate(MMA), 3-(trimethoxysilyl) propyl methacrylate(TMSPM) and 2-(cinnamoyloxy)ethyl methacrylate(CEMA). Photocrosslinkable copolymer composed of MEPAB/MMA/TMSPM/CEMA＝70/20/0/10 were used for humidity-sensitive membrane, and those of 50/0/20/30 and 0/0/50/50 were used for polymeric anchoring agents. 3- (Triethoxysilyl)propyl cinnamate(TESPC) was also used as a surface-pretreating agent for the comparison of capability of attachment of polyelectrolyte to the electrode surface with polymeric photocurable silanecoupling agents. Pretreatment of the electrode substrate with anchoring agents was performed to form a cinnamate thin film on the electrode through covalent bonds. When the sensors were irradiated with UV light, the anchoring of a polyelectrolyte into the substrate was carried out via the [2$\pi$+2$\pi$] cycloaddition. The resulting sensors using polymeric anchoring agents and TESPC showed water durability with increase of resistance by 60~85%, which is corresponding to the reduction of 2.25~3.15%RH, after soaking in water for 24 h. They showed good hysteresis (-0.2%RH), response time (90 sec) and long-term stability at high temperature and humidity.

• Polymer(Korea)
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• v.34 no.6
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• pp.565-573
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• 2010

Copoly(2-(dimethylamino)ethyl methacrylate)(DAEMA)/butyl acrylate (BA) and copoly(methyl methacrylate)(MMA)/BA/2-(cinnamoyloxy)ethyl methacryate (CEMA), which were cross-linked with dibromoalkane and UV irradiation, respectively, were prepared for the precursors of interpenetrating polymer network (IPN) humidity-sensitive films. 3-(Triethoxysilyl)propyl cinnamate (TESPC) was used as a surface-pretreating agent for the attachment of IPN-polyelectrolyte to the electrode surface by UV irradiation. Humidity sensitive polymeric thin films with an IPN structure were prepared by crosslinking reactions of copoly(DAEMA/BA) with 1,4-dibromobutane (DBB) and copoly(MMA/BA/CEMA) by UV-irradiation. The anchoring of an IPN-polyelectrolyte into the substrate was carried out via the photochemical $[2{\pi}+2{\pi}]$ cycloaddition. The resulting humidity sensors showed a high sensitivity in the range of 20~95%RH and a small hysteresis (<1.5%RH). The response time for adsorption and desorption process at 33~94%RH was 48 and 65 s, respectively, indicating a fast response. The effects of the concentration of copolymers, molar ratio of crosslinking agents and time of the precursor solution for dip-coating on their humidity sensitive properties including water durability were investigated.