• Journal of the Korean Ceramic Society
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• v.53 no.3
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• pp.367-375
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• 2016

A novel strategy for the synthesis of $CoSb_2$ nanoparticles is demonstrated via preparation of novel organometallic complexes. Hydrated cobalt oleate (CoOl) and non-hydrated antimony oleate (SbOl) complexes are synthesized as precursors. The $CoSb_2$ nanoparticles are prepared by hot injection, which involves thermolysis of CoOl and SbOl in a non-coordinating solvent at $320^{\circ}C$. The coordination modes and distinct thermal behaviors of the intermediate non-hydrated SbOl complexes are comparatively investigated by thermo-analytical techniques. When the reaction temperature is increased, the particle size is found to increase linearly. The crystallinity of the $CoSb_2$ nanoparticles prepared at $250^{\circ}C$ is amorphous phase without any peaks. $CoSb_2$ structural peaks start to appear at $300^{\circ}C$ and dominant peaks with high crystallinity are synthesized at $320^{\circ}C$. The potential chemical structures of non-hydrated SbOl and their reaction mechanisms by thermolysis are elucidated. The elemental composition and crystallographic structure of $CoSb_2$ nanoparticles suggest a bimodal interaction of the organic shell and the nanoparticle surface, with a chemical absorbed inner layer and physically absorbed outer layer of carboxylic acid.

• Bulletin of the Korean Chemical Society
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• v.26 no.11
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• pp.1776-1782
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• 2005

ZnSe/ZnS, UV-blue luminescent core shell quantum dots, were synthesized via a thermal decomposition reaction of organometallic zinc and solvent coordinated Selenium (TOPSe) in a hot solvent mixture. The synthetic conditions of the core (ZnSe) and the shell (ZnS) were independently studied at various reaction temperature conditions. The obtained colloidal nanocrystals at corresponding temperatures were characterized for their optical properties by UV-vis, room temperature solution photoluminescence (PL) spectroscopy, and further obtained powders were characterized by XRD, TEM, and EDXS analyses. The synthetic temperature condition to obtain the best PL emission intensity for the ZnSe core was 300 ${^{\circ}C}$, and for the optimum shell capping, the temperature was 135 ${^{\circ}C}$. At this temperature, solution PL spectrum showed a narrow emission peak at 427 nm with a PL efficiency of 15%. In addition, the measured particle sizes for the ZnSe/ZnS nanocomposite via TEM were in the range of 5 to 12 nm. Furthermore, we have synthesized water-soluble ZnSe/ZnS nanoparticles by capping the ZnSe/ZnS hydrophobic surface with mercaptoacetate (MAA) molecules. For the obtained aqueous colloidal solution, the UV-vis spectrum showed an absorption peak at 250 nm, and the solution PL emission spectrum showed a peak at 425 nm, which is similar to that for hydrophobic quantum dot ZnSe/ZnS. However, the calculated PL efficiency was relatively low (0.1%) due to the luminescence quenching by water and MAA molecules. The capping ligand was also characterized by FT-IR spectroscopy, with the carbonyl stretching peak in the mercaptoacetate molecule appearing at 1575 $cm ^{-1}$. Finally, the particle sizes of the MAA capped ZnSe/ZnS were measured by TEM, showing a range of 12 to 17 nm.

• Bulletin of the Korean Chemical Society
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• v.31 no.7
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• pp.1997-2002
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• 2010

ZnSe and ZnS:Mn nanocrystals were synthesized via the thermal decomposition of their corresponding organometallic precursors in a hot coordinating solvent (TOP/TOPO) mixture. The organic surface capping agents were substituted with EDTA molecules to impart hydrophilic surface properties to the resulting nanocrystals. The optical properties of the water-dispersible nanocrystals were analyzed by UV-visible and room temperature solution photoluminescence (PL) spectroscopy. The powders were characterized by X-ray diffraction (XRD), high resolution transmission electron microscopy (HR-TEM), and confocal laser scanning microscopy (CLSM). The solution PL spectra revealed emission peaks at 390 (ZnSe-EDTA) and 597 (ZnS:Mn-EDTA) nm with PL efficiencies of 4.0 (former) and 2.4% (latter), respectively. Two-photon spectra were obtained by fixing the excitation light source wavelengths at 616 nm (ZnSe-EDTA) and 560 nm (ZnS:Mn-EDTA). The emission peaks appeared at the same positions to that of the PL spectra but with lower peak intensity. In addition, the morphology and sizes of the nanocrystals were estimated from the corresponding HR-TEM images. The measured average particle sizes were 5.4 nm (ZnSe-EDTA) with a standard deviation of 1.2 nm, and 4.7 nm (ZnS:Mn-EDTA) with a standard deviation of 0.8 nm, respectively.

• Korean Journal of Crystallography
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• v.18 no.1_2
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• pp.1-6
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• 2007

An Organometallic compound, $C_{16}H_{35}B_{10}IrS_2Si$, was synthesized from o-carborane, $Cp^*Ir(S_2C_2B{10}H_{10})$, and $Me_3SiCHN_2$. The molecular structure of this complex has been determined by X-ray diffraction. Crystallographic data : monoclinic, space group $P2_1/n$, $a=10.1986(12)\;{\AA}$, $b=14.834(5)\;{\AA}$, $c=17.139\;{\AA}$, ${\beta}=92.24(2)^{\circ}$, Z=4, $V=2591.0(14)\;{\AA}^3$. The structure was solved by direct methods and refined by full-matrix leat-squares methods to give a model with a reliability factor R=0.053 for 5080 reflections.

• Journal of Photoscience
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• v.10 no.2
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• pp.185-187
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• 2003

The preparation and the photophysics of organometallic Pt(II) and Ir(III) complexes with 6-ch1oro-3-phenylpyridazine (H6Clppdz) are reported. $K_2$PtCl$_4$ and IrCl$_3$ㆍn$H_{2}O$ cleanly cyclometalate with H6Clppdz, forming the corresponding chloro-bridged dimers, (6Clppdz)Pt($\mu$-Cl)$_2$Pt(6Clppdz) and (6Clppdz)$_2$Ir($\mu$-Cl)$_2$Ir(6Clppdz)$_2$ in good yield. These chloro-bridged dimers are cleaved with acetylacetone (Hacac) to give the corresponding monomer, (6Clppdz)Pt(acac) and (6Clppdz)$_2$ Ir(acac), respectively. Both complexes show bright orange luminescence at room temperature and the emission wavelengths are different depending on the metal and the structure of complexes. (6Clppdz)Pt(acac) shows two sharp emission bands in shorter wavelength ($\lambda$$_{em}$=541 and 580 nm), while (6Clppdz)$_2$ Ir(acac) shows a broad emission band in longer wavelength ($\lambda$$_{em}$=615 nm). Strong spinorbit coupling due to the heavy metal atom allows for the formally forbidden mixing of the $^1$MLCT with the $^3$MLCT and $^3$$\pi$-$\pi$$^{*}$ states.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.18 no.2
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• pp.62-67
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• 2008

An Organometallic compound, $C_{12}H_{20}B_{10}S_2Co_2$, was synthesized from o-carborane, $Cp^*Co(S_2B_2B_{10}H_{10})$ and $BH_3{\cdot}THF$. The molecular structure of this complex has been determined by X-ray diffraction. Crystallographic data: monoclinic, space group Cc, a=15.981(4) ${\AA}$, b=15.478(17) ${\AA}$, c=12.0562(17) ${\AA}$, ${\beta}=115.063(16)^{\circ}$, Z=4, V=9683(4) ${\AA}^3$. The structure was solved by direct methods and refined by full-matrix leat-squares methods to give a model with a reliability factor R = 0.0630 for 9948 reflections.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.08a
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• pp.198-198
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• 2011

Organocatalysis is a relatively new and popular area within the field of chiral molecule synthesis. It is one of the main branches of enantioselective synthesis with enzymatic and organometallic catalysis. In recent years, immense high quality studies on catalysis by chiral secondary amines were reported. These progresses instantly led to different organocatalytic activation concepts, so thousands of researchers from academia and the chemical industry are currently involved in this field and new ideas, new approaches, and creative thinking have been rapidly emerged. Organocatalysts, some of which are natural products, appear to solve the problems of metal catalysts. Compared to metal-based catalysis, they have many advantages including savings in cost, time, and energy, easier experimental procedure, and reduction of chemical waste. These benefits originate from the following factors. First, organocatalysts are generally stable in oxygen and water in the atmosphere, there is no need for special equipments or experimental techniques to operate under anhydrous or anaerobic conditions. Second, organic reagents are naturally available from biological materials as single enantiomers that they are easy and cheap to prepare which makes them suitable for small-scale to industrial-scale reactions. Third, in terms of safety related catalysis, small organic molecules are non-toxic and environmentally friendly. Therefore, the purpose of this research is to develop novel synthetic methods and design for various organocatalyst. Furthermore, it is expected that these organocatalysts can be applied to a variety of asymmetric reactions and study the transition state of these reactions using a metal sulface. Here, we report the synthesis of unprecedented organocatalysts, proline and pyrrolidine derivatives with quaternary carbon center.

• Journal of the Korean Chemical Society
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• v.7 no.3
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• pp.216-224
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• 1963

Reaction of organic chlorine containing ester, alcohol, and acids with metallic tin and zinc in dimethyl formamide solvent gave a good yield of organo metallic complex. The same reaction under a mixed U.V. irradiation could not give an appreciable yield of the complex except in the case of an elevated reaction temperature. The solvation effect of dimethyl formamide of the metallic complex formation was markedetly increased as compared to the reaction in toluene and cyclohexane. In case of chlorine containing carboxylic acid, the formation of organo chloro zinc complex of the salt was observed. The reaction of organo zinc complex with a carbonyl precursor gave the addition product together with a dimerized product. Especially the aldehyde species enhanced the formation of zinc complex. The addition reaction was simple and convenient, but the yield was not high.(30-40% for the acid, 73% for the ester, 14.6% for alcohol). The result was discussed on basis of solvent effect and the procedures were described.

• Korean Journal of Crystallography
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• v.15 no.2
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• pp.83-87
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• 2004

An organometallic complex. $Me_2Pt(PPh_2CH_2C(t-Bu)=N-N=CMe(2-py)-\kappa^2N,P)$ was synthesized from phosphinohydrazone $Ph_2PCH_2C(t-Bu)=NNH_2$, 2-acetylpyridine, and $[PtMe2({\mu}-SMe_2)]_2$. The molecular structure of this complex has been determined by X-ray diffraction. Crystallographic data: monoclinic, space group $P2_1/n,\;a=11.6926(7)\;{\AA},\;b=15.6607(19)\;{\AA},\; c=14.6125(6)\;{\AA},\;\beta=93.018(4)^{\circ},\;Z=4,\;V=2672.0(4)\;{\AA}^3$. The structure was solved by direct methods and refined by full-matrix least-squares methods to give a model with a reliability factor R = 0.0363 for 5238 reflections.

• Korean Journal of Crystallography
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• v.15 no.2
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• pp.88-92
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• 2004

An organometallic compound, $(C_{16}H_{21}B_{10}BrOSn)$, was synthesized from o-carborane, closo-1-[(methoxyl)methyl]-o-carborane $(HCab^o)$, and $SnMe_2Br_2$. The molecular structure of this complex has been determined by X-ray diffraction. Crystallographic data: orthorhombic, space group Pna2, a = 17.9292(15)$\AA$, b= 7.2066(4)$\AA$, c=13.0582(10)$\AA$, Z=4, V=1687.2(2) $\AA^3$. The structure was solved by direct methods and refined by full-matrix least-squares methods to give a model with a reliability factor R=0.0574 for 1724 reflections.