• Proceedings of the Korean Vacuum Society Conference
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• 2014.02a
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• pp.103.1-103.1
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• 2014

Due to their excellent optical and electrochemical properties, conjugated polymers have attracted much attention over the last two decades and employed to opto-electrical devices. In particular, conjugated polymers possess many attractive features that make them suitable for a variety of sensing task. For example, their delocalized electronic structures can be strongly modified by varying the surrounding environment, which significantly affected molecular energy level. In other word, conjugated polymers can detect and transduce the environmental information into a fluorescence signal. Conjugated polymers also display amplified quenching compared to small molecule counterparts. This amplified fluorescence quenching is attributed to the delocalization and migration of the excitons along the conjugated polymer backbones. Long backbones of conjugated polymer provide the transporting path for electron as a conduit, allowing that excitons migrate rapidly into quencher site along the backbone. This is often referred to as the molecular wire effect or antenna effect. Moreover, structures of conjugated polymers can be easily tailored to adjust solubility, absorption/emission properties, and regulation of electron/energy transfer. Based on this versatility, conjugated polymers have been utilized to many novel sensory platforms as a promising material. In this tutorial, I will highlight a variety of fluorescence sensors base on conjugated polymer and explain their sensory mechanism together with selected examples from reference literatures.

• Textile Coloration and Finishing
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• v.25 no.2
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• pp.89-93
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• 2013

The electrochemical study has been enjoyed in many areas of chemistry. Through this approach using electrochemical measurement, empirical HOMO and LUMO values can be calculated by three methods such as absorption measurement, cyclicvoltammetry and computational calculations. In this study, 1,3-bisdicyanovinylindane was prepared and investigated toward its optical properties. The absorption intensities were changed depending on changes of pH. These absorption changes are induced by resonance form of 1,3-bisdicyanovinylindane. The electron delocalization in ${\pi}$ system is related to the resonance form. In according to this electron density distribution and HOMO/LUMO values of 1,3-bisdicyanovinylindane were simulated and calculated by Material Studio 4.3, absorption measurement and cyclicvoltammograms. The 1,3-bisdicyanovinylindane is one of the most attracted acceptor units in D-${\pi}$-A system. This attempt is useful to determine more detailed characteristics of the energy potentials.

• Bulletin of the Korean Chemical Society
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• v.19 no.3
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• pp.349-353
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• 1998

Solvolysis rates of substituted 2-aryl-1,1-dimethylethyl bromides (1) were determined in a variety of solvents such as aqueous mixtures of ethanol, acetone, 2,2,2-trifluoroethanol, and also mixtures of ethanol and TFE at 25 ℃, 35 ℃, and 45 ℃. The solvent effects were analyzed in terms of Winstein-Grunwald equation. The solvent effects of 1-4-MeO failed to give a single linear correlation against either Y or YCl (YBr), but exhibited a wide split pattern which could not be related to the solvent nucleophilicity. On the other hand 1-4-CH3 and 1-H gave a fairly good linearity. In the case of 1-4-MeO, a fairly good linearity was observed against YΔ defined from the solvolysis of 4-methoxyneophyl tosylate. It is assumed that resonance interaction between reaction site and aryl-π-system operates to give charge delocalization regardless of the different solvolysis mechanisms. The Hammett-Brown treatment of the solvolytic rate constant of compounds 1 was obtained non-linear two separated lines of - 1.06 to - 1.46, suggesting of mechanistic changeover from kc-ks to kΔ on going from electron-withdrawing to electron-donating substituents as a basis of 4-CH3 group.

• Bulletin of the Korean Chemical Society
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• v.25 no.4
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• pp.452-459
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• 2004

The geometrical structures of various isomers of hexafluoro-1,3-butadiene (HFBD), tetrafluoro-1,3-butadiene (TFBD), and difluoro-1,3-butadiene (DFBD) have been studied theoretically. Natural steric and natural resonance theory (NRT) analyses indicate that the lower energy of skew s-cis conformer of hexafluoro-1,3-butadiene than that of the s-trans conformer is originated from the strong steric repulsions between fluorine atoms particularly in the s-trans conformer. The resonance structures generated by NRT also show that the lone electron pairs of fluorine atoms effectively extend the conjugation, and the large differences in energy among the structural isomers of tetrafluoro-1,3-butadiene and difluoro-1,3-butadiene are in part attributed to the differences in the delocalization energies, in addition to the steric repulsion between fluorine atoms. Other interatomic interactions, such as hydrogen bonding, also play important roles in determination of the structures of isomers of tetrafluoro-1,3-butadiene and difluoro-1,3-butadiene.

• Bulletin of the Korean Chemical Society
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• v.24 no.8
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• pp.1215-1218
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• 2003

An analysis of the bonding situation in CaM₂P₂ (M=Fe, Ni) with ThCr₂Si₂ structure is made in terms of DOS and COOP plots. The main contributions to covalent bonding are due to M-P and P-P interactions in both compounds. Particularly, the interlayer P-P bonding by variation in the transition metal is examined in more detail. It turns out that the shorter P-P bonds in CaNi₂P₂ form as a result of the decreasing electron delocalization into ${{\sigma}_p}^*$ of P₂ due to the weaker bonding interaction between the metal d and ${{\sigma}_p}^*$ as the metal d band is falling from Fe to Ni.

• 한국전기화학회:학술대회논문집
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• 2005.07a
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• pp.329-334
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• 2005

In order to find out rational design and synthetic strategies toward efficient hydrogen storage materials, we performed quantum mechanical calculations on a series of the Metal-Organic Frameworks (MOFs) containing functionalized organic linkers. Based on the shape of frontier orbitals and the electrostatic potential map of various MOFs from density functional theory calculations, it was found that the delocalization of electron and asymmetric polarization of the organic linker play an important role in the hydrogen storage capacity of Metal-Organic Frameworks. The prediction of the modeling study could be supported by the hydrogen adsorption experiments using MOF-5 and amine substituted MOF-5, which showed more enhanced hydrogen storage capacity of amine substituted MOF-5 compared with that of MOF-5.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 1993.11a
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• pp.90-92
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• 1993

PM3 semiempirical calculations ions have performed on the three aromatic heterocyclic polymers. The dipole moment (${\mu}$7), static 1st-orders(${\alpha}$), 2nd-order (${\beta}$), and 3rd-order polarizabilities(${\gamma}$) were investigated to study the nonlinear optical properties of the polythiophene, polyfuran, and polypyrrole systems. As a function of n, ${\alpha}$ and ${\gamma}$ increases much more rapidly for the polythiophene systems than for the polyfuran and Polypyrrole systems due to the pi-electron delocalization.

• Bulletin of the Korean Chemical Society
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• v.31 no.4
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• pp.781-788
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• 2010

Experimental and theoretical studies show that all covalent azides possess a nonlinear azide group. They also rationalize this remarkable structural feature. We have seen that the most important non-covalent contributions in the covalently bound azides system (X-N1-N2-N3) are the $\pi$-delocalization over the entire molecule and a strong negative hyperconjugation which donates electron density from the filled $\sigma$ (X-N1) orbital into the unfilled, antibonding $\pi^*$ (N2-N3) orbital. For transition metal azide complexes, a bent configuration and a small difference between the N-N bond lengths, generally the longer one being adjacent to the transition metal, were observed.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.17 no.6
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• pp.652-660
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• 2004

The cis-hex-3-ene-1,5-diynyl-bridged diiron compound 3, [(η$^{5}$ - $C_{5}$ M $e_{5}$ ) Fe(dppe)］$_2$($\mu$-C≡C-CH=CH-C≡C), have been prepared and characterized by cyclic voltammetry(CV), and electronic spectroscopy (UV-VIS and near-IR, NMR). From the results, compound 3 show two well resolved, single-electron, reversible oxidation waves by CV, and comproportionation constant(Kc) calculated from the CV data for compound 3. The Mixed-valence (MV) radical cation 3$^{+}$ show strong absorptions in the near IR, 1586 nm, and this band is more readily assigned as MV $\pi$-$\pi$ band of delocalized complex (Robin-Day Mixed-valence Class III), and the $H_{ab}$ , effective coupling parameter are most consistent with electronic delocalization.

• Bulletin of the Korean Chemical Society
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• v.16 no.2
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• pp.89-95
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• 1995

The adsorption of methanethiol and benzenethiol on Ag(111) and Ag(100) surfaces is studied respectively, employing ASED (Atom Superposition and Electron Delocalization) method. Metal surfaces are modelled by 3-layer clusters. The corresponding thiolate anions are taken as adsorbates. The highly coordinated binding sites are most favored for both surfaces. The tilted angles of C-S axis from the surface normal are nearly zero. There's Charge transfer from adsorbate to substrate and the stretching frequency of C-S bond upon adsorption is blue-shifted from its gas phase counterpart, and its amount is the smallest at most highly coordinated site. FMO (Fragment Molecular Orbital) analysis of the system give the explanation for these results.