• Bulletin of the Korean Chemical Society
• /
• v.25 no.9
• /
• pp.1314-1320
• /
• 2004

The adsorption and configuration of CO molecules adsorbed on W (110) and W (100) surfaces have been calculated by the atomic superposition and electron delocalization molecular orbital (ASED-MO) method. Referred to as the ASED-MO method, it has been used in the present study to calculate the geometries, binding energies, vibrational frequencies, orbital energies, reduced overlap population (ROP), and charges. From these results adsorption properties of ${\alpha}$-state and ${\beta}$-state were deduced. The calculated binding energies are in good agreement with the experimental result. On the W (110), the calculated average binding energies are 2.56 eV for the end-on configuration and 3.20 eV for the lying-down configuration. Calculated vibrational frequency is 1927 $cm^{-1}$ at a 1-fold site and 1161 $cm^{-1}$ at a long-bridge (2) site. These results are in reasonable agreement with experimental values. On the W(100) surface, calculated average binding energies of the end-on and the lying-down are 2.54 eV and 4.02 eV respectively. The differences for binding energy and configuration on the surfaces are explained on the basis of surface-atom coordination and atom-atom spacing. In the favored lyingdown CO configuration on the W(110) and W(100) surfaces, 4 ${\sigma}$ and 1 ${\pi}$ donation interactions, coupled with the familiar 5 ${\sigma}$ donation to the surfaces and back-donations to the CO 2 ${\pi}^{\ast}$ orbital, are responsible for adsorption to the surface.

• Bulletin of the Korean Chemical Society
• /
• v.10 no.2
• /
• pp.191-196
• /
• 1989

We obtained the new complexes, $Fe{\eta}^4-R,R'-TPSCp](CO)_3$(R,R'-TPSCp = 1,1-disubstituted 2,3,4,5-Tetraphenyl-1-Silacyclopenta-2,4-diene; R = Ph, R' = Cl, R = R' = Cl) from the reaction of the corresponding R,R'-TPSCp with ironpentacarbonyl under reflux in toluene. Also, the analogous complexes with R = R' = Me and R = Me, R' = Cl were obtained in an identical manner. We have determined the crystal structure of $Fe[Ph(Cl)-TPSCp](CO_)3$ by using Mo ka, ${\lambda}$ = 0.71069${\AA}$, where the unit cell was found to be monoclinic with a = 9.042 (6)${\AA}$, b = 19.870 (9)${\AA}$, c = 17.426 (9)${\AA}$ and ${\beta}$ = 96.28(4)$^{\circ}$. The butadiene moiety of TPSCp ring is planar and the dihedral angle of the butadiene plane and C4-Si-C25 plane was opened up to 41.8$^{\circ}$. The C-C distances in the butadiene moiety were found to be 1.4346, 1.462, and 1.440 ${\AA}$, respectively. It may be said that the four ${\pi}$-electrons are delocalized over the four carbons in five membered ring through coordination with ironcarbonyl. In this complex Fe is either in distorted tetrahedron environment with the centroid of the four C-atom butadiene moiety and three carbons of the three carbonyls or in distorted square-pyramidal environment with two midpoints of double bonds of the butadiene moiety and two carbons of carbonyl defining the base of the pyramid and the carbon of remaining carbonyl the apex.

• Bulletin of the Korean Chemical Society
• /
• v.27 no.5
• /
• pp.679-686
• /
• 2006

The positions of $PbI _2$ molecule synthesized into the molecular-dimensioned cavities of $\mid K_6 (Pb _4I_2)(PbI_2) _{0.67}-(H_2O)_2\mid [Si _{12}Al _{12}O _{48}]$-LTA have been determined. A single crystal of $\mid Pb _6\mid [Si _{12}Al _{12}O _{48}]$-LTA, prepared by the dynamic ion-exchange of $\mid Na _{12}\mid [Si _{12}Al _{12}O _{48}]$-LTA with aqueous 0.05 M $Pb _(NO _3)_2$ and washed with deionized water, was placed in a stream of flowing aqueous 0.05 M KI at 294 K for three days. The resulting crystal structure of the product $( \mid K_6 (Pb _4I_2)(PbI_2) _{0.67}(H_2O)_2\mid [Si _{12}Al _{12}O _{48}]$-LTA, a = 12.353(1) $\AA$) was determined at 294 K by single-crystal X-ray diffraction in the space group Pm3 m. It was refined with all measured reflections to the final error index $R_1$ = 0.062 for 623 reflections which $F_o$ > 4$\sigma$($F_o$). 4.67 $Pb ^{2+}$ and six $K^+$ ions per unit cell are found at three crystallographically distinct positions: 3.67 $Pb ^{2+}$ and three $K^+$ ions on the 3-fold axes opposite six-rings in the large cavity, three $K^+$ ions off the plane of the eight-rings, and the remaining one $Pb ^{2+}$ ion lies opposite four-ring in the large cavity. 0.67 $Pb ^{2+}$ ions and 1.34 $I^-$ ions per unit cell are found in the sodalite units, indicating the formation of a $PbI _2$ molecule in 67% of the sodalite units. Each $PbI _2$ (Pb-I = 3.392(7) $\AA$) is held in place by the coordination of its one $Pb ^{2+}$ ion to the zeolite framework (a $Pb ^{2+}$ cation is 0.74 $\AA$ from a six-ring oxygens) and by the coordination of its two $I^-$ ions to $K^+$ ions through six-rings (I-K = 3.63(4) $\AA$). Two additional $I^-$ ions per unit cell are found opposite a four-ring in the large cavity and form $Pb _2K_2I^{5+}$ and $Pb _2K_2I^{3+}$ moieties, respectively, and two water molecules per unit cell are also found on the 3-fold axes in the large cavity.

• Journal of the Korean Chemical Society
• /
• v.61 no.1
• /
• pp.29-33
• /
• 2017

Formation of Au particles in nonstoichiometric $Cu_{2-x}{^I}Cu{_2}^{II}O_{3-{\delta}}$ ($x{\approx}0.20$; ${\delta}{\approx}0.10$) oxide from aniline + hydrochloric acid mixtures and chloroauric acid in the ratios 30 : 1; 60 : 1; 90 : 1 (S1-S3) by volume and 0.01 mol of copper acetate, $Cu(OCOCH_3)_2.H_2O$, in each case is performed by sol-gel growth. Powder x-ray diffraction (XRD) results show Au particles are dispersed in tetragonal nonstoichiometric dicopper (I) dicopper (II) oxides, $Cu_{2-x}{^I}Cu{_2}^{II}O_{3-{\delta}}$ ($x{\approx}0.20$; ${\delta}{\approx}0.10$). Average crystallite sizes of Au particles determined using Scherrer equation are found to be in the approximate ranges ${\sim}85-140{\AA}$, ${\sim}85-150{\AA}$ and ${\sim}80-150{\AA}$ in S1-S3, respectively which indicate the formation of Au nano-micro size particles in $Cu_{2-x}{^I}Cu{_2}^{II}O_{3-{\delta}}$ ($x{\approx}0.20$; ${\delta}{\approx}0.10$) oxides. Hysteresis behaviour at 300 K having low loop areas and magnetic susceptibility values ${\sim}5.835{\times}10^{-6}-9.889{\times}10^{-6}emu/gG$ in S1-S3 show weakly ferromagnetic nature of the samples. Broad and isotropic electron paramagnetic resonance (EPR) lineshapes of S1-S4 at 300, 77 and 8 K having $g_{iso}$-values ${\sim}2.053{\pm}0.008-2.304{\pm}0.008$ show rapid spin-lattice relaxation process in magnetic $Cu^{2+}$ ($3d^9$) sites as well as delocalized electrons in Au ($6s^1$) nano-micro size particles in the $Cu_{2-x}{^I}Cu{_2}^{II}O_{3-{\delta}}$ ($x{\approx}0.20$; ${\delta}{\approx}0.10$) oxides. Broad and weak UV-Vis diffuse reflectance optical absorption band ~725 nm is assigned to $^2B_{1g}{\rightarrow}^2A_{1g}$ transitions, and the weak band ~470 nm is due to $^2B_{1g}{\rightarrow}^2E_g$ transitions from the ground state $^2B_{1g}$(${\mid}d_{x^2-y^2}$>) of $Cu^{2+}$ ($3d^9$) ions in octahedral coordination having tetragonal distortion.

• Bulletin of the Korean Chemical Society
• /
• v.33 no.5
• /
• pp.1491-1504
• /
• 2012

InP quantum dot (QD)-organosilicon nanocomposites were synthesized and their photoluminescence quenching was mainly investigated because of their applicability to white LEDs (light emitting diodes). The as-synthesized InP QDs are capped with myristic acid (MA), which are incompatible with typical silicone encapsulants. We have introduced a new ligand, 3-aminopropyldimethylsilane (APDMS), which enables embedding the QDs into vinyl-functionalized silicones through direct chemical bonding. The exchange of ligand from MA to APDMS does not significantly affect the UV absorbance of the InP QDs, but quenches the PL to about 10% of its original value with the relative increase in surface related emission intensities, which is explained by stronger coordination of the APDMS ligands to the surface indium atoms. InP QD-organosilicon nanocomposites were synthesized by connecting the QDs using a short cross-linker such as 1,4-divinyltetramethylsilylethane (DVMSE) by the hydrosilylation reaction. The formation and changes in the optical properties of the InP QD-organosilicon nanocomposite were monitored by ultraviolet visible (UV-vis) absorbance and steady state photoluminescence (PL) spectroscopies. As the hydrosilylation reaction proceeds, the QD-organosilicon nanocomposite is formed and grows in size, causing an increase in the UV-vis absorbance due to the scattering effect. At the same time, the PL spectrum is red-shifted and, very interestingly, the PL is quenched gradually. Three PL quenching mechanisms are regarded as strong candidates for the PL quenching of the QD nanocomposites, namely the scattering effect, F$\ddot{o}$rster resonance energy transfer (FRET) and cross-linker tension preventing the QD's surface relaxation.

• Journal of the Korean Chemical Society
• /
• v.59 no.3
• /
• pp.215-224
• /
• 2015

Unsymmetrical tetradentate Schiff base N-(2-hydroxy-5-methylacetophenone)-N'-(2-hydroxy acetophenone) ethylene diamine (H₂L) and its complexes with Cr(III), Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) have been synthesized and characterized by elemental analyses, magnetic susceptibility measurements, IR, electronic spectra and thermogravimetric analyses. ¹H, ¹³C-NMR and FAB Mass spectra of ligand clearly indicate the presence of OH and azomethine groups. Elemental analyses of the complexes indicate that the metal to ligand ratio is 1:1 in all complexes. Infrared spectra of complexes indicate a dibasic quadridentate nature of the ligand and its coordination to metal ions through phenolic oxygen and azomethine nitrogen atoms. The thermal behavior of these complexes showed the loss of lattice water in the first step followed by decomposition of the ligand in subsequent steps. The thermal data have also been analyzed for the kinetic parameters by using Horowitz-Metzger method. The dependence of the electrical conductivity on the temperature has been studied over the temperature range 313-403 K and the complexes are found to show semiconducting behavior. XRD and SEM images of some representative complexes have been recorded. The antimicrobial activity of the ligand and its complexes has been screened against various microorganisms and all of them were found to be active against the test organisms. The Fe(III) and Ni(II) complex have been tested for the catalytic oxidation of styrene.

• Journal of the Korean Chemical Society
• /
• v.56 no.6
• /
• pp.679-691
• /
• 2012

New series of metal complexes of Co(II), Ni(II), Cu(II), Zn(II), Pd(II) and Pt(II) with 4-(p-chlorophenyl)-1-(pyridin-2-yl)thiosemicarbazide (HCPTS) have been synthesized and characterized by elemental analyses, magnetic moment, spectra (IR, UV-Vis, $^1H$ NMR, mass and ESR) and thermal studies. The IR data suggest different coordination modes for HCPTS which behaves as a monobasic bidentate with all metal ions except Cu(II) and Zn(II) which acts as a monobasic tridentate. Based on the electronic and magnetic studies, Co(II), Cu(II), Pd(II) and Pt(II) complexes have square - planner, Ni(II) has mixed stereochemistry (tetrahedral + square planar), while Zn(II) is tetrahedral. Molar conductance in DMF solution indicates the non-ionic nature of the complexes. The ESR spectra of solid copper(II) complex show $g_{\parallel}$ (2.2221) > $g_{\perp}$ (2.0899) > 2.0023 indicating square-planar structure and the presence of the unpaired electron in the $d_x2_{-y}2$ orbital with significant covalent bond character. The thermal stability and degradation kinetics of the ligand and its metal complexes were studied by TGA and DTA and the kinetic parameters were calculated using Coats-Redfern and Horowitz-Metzger methods. The complexes have more antibacterial activity against some bacteria than the free ligand. However, the ligand has high anticancer activities against HCT116 (human colon carcinoma cell line) and HEPG2 (human liver hepatocellular carcinoma cell line) compared with its complexes.

• Bulletin of the Korean Chemical Society
• /
• v.33 no.3
• /
• pp.911-916
• /
• 2012

Ion selectivity in a simple cyclic peptide nanotube, composed of four cyclo[-(D-Ala-Glu-D-Ala-Gln)$_2-$] units, is investigated by calculating the PMF profiles of $Na^+$, $K^+$, and $Cl^-$ ions permeating through the peptide nanotube in water. The final PMF profiles of the ions obtained from the umbrella sampling (US) method show an excellent agreement with those from the thermodynamic integration (TI) method. The PMF profiles of $Na^+$ and $K^+$ display free energy wells while the PMF curve of $Cl^-$ features free energy barriers, indicating the selectivity of the cyclic peptide nanotube to cations. Decomposition of the total mean force into the contribution from each component in the system is also accomplished by using the TI method. The mean force decomposition profiles of $Na^+$ and $K^+$ demonstrate that the dehydration free energy barriers by water molecules near the channel entrance and inside the channel are completely compensated for by attractive electrostatic interactions between the cations and carbonyl oxygens in the nanotube. In the case of $Cl^-$, the dehydration free energy barriers are not eliminated by an interaction between the anion and the peptide nanotube, leading to the high free energy barriers in the PMF profile. Calculations of the coordination numbers of the ions with oxygen atoms pertaining to either water molecules or carbonyl groups in the peptide nanotube reveal that the stabilization of the cations in the midplane regions of the nanotube arises from the favorable interaction of the cations with the negatively charged carbonyl oxygens.

• Bulletin of the Korean Chemical Society
• /
• v.26 no.12
• /
• pp.1969-1974
• /
• 2005

Composite systems of $Eu(phen)_2Cl_3{(H_2O)}_2$, Eu(DN-bpy)$(phen)Cl_3{(H_2O)}_2$ and Eu(DB-bpy)$(phen)Cl_3{(H_2O)}_2$ (DNbpy: $4,4^\prime$-Dinonyl-$2,2^\prime$-dipyridyl; DB-bpy: $4,4^\prime$-Di-tert-butyl-$2,2^\prime$-dipyridyl) with crown ethers of Benzo-15-crown-5 (B15C5), Benzo-18-crown-6 (B18C6), 18-crown-6 (18C6), Dibenzo-18-crown-6 (DB18C6) and Dibenzo-24-crown-8 (DB24C8) were fabricated successfully and characterized by using photoluminescent spectroscopy and luminescent lifetime measurements. All composites formed show high luminescence mainly in red region. It was found that the heterocyclic ligands such as phen, DN-bpy and DB-bpy as well as the crown ethers have great influences on the photoluminescent properties of $Eu^{3+}$ ion. The environment around $Eu^{3+}$ ion in the composite systems changes greatly,presumably the variation of the first coordination sphere. The $Eu^{3+}$ ion occupies higher symmetrical environment and in more than one kind of symmetrical site in the composite systems studied in this work.

• Journal of the Korean Magnetic Resonance Society
• /
• v.14 no.2
• /
• pp.55-75
• /
• 2010

An ion-exchanged reaction of $MnCl_2$ with Al-incorporated solid core/mesoporous shell silica (AlSCMS) followed by calcinations generated manganese species, where average oxidation state of manganese ion is 3+, in the mesoporous materials. Dehydration results in the formation of $Mn^{2+}$ ion species, which can be characterized by electron spin resonance (ESR). The chemical environments of the manganese centers in Mn-AlSCMS were investigated by diffuse reflectance, UV-VIS and ESR spectroscopic methods. Upon drying at 323 K, part of manganese is oxidized to higher oxidation state ($Mn^{3+}$ and $Mn^{4+}$) and further increase in (average) oxidation state takes place upon calcinations at 823 K. It was found that the manganese species on the wall of the Mn-AlSCMS were transformed to tetrahedral $Mn^{3+}$ or $Mn^{4+}$ and further changed to square pyramid by additional coordination to water molecules upon hydration. The oxidized $Mn^{3+}$ or $Mn^{4+}$ species on the surfaces were reversibly reduced to $Mn^{2+}$ or $Mn^{3+}$ species or lower valances by thermal process. Mn(II) species I with a well resolved sextet was observed in calcined, hydrated Mn-AlSCMS, while Mn (II) species II with g = 5.1 and 3.2 observed in dehydrated Mn-AlSCMS. Both species I and II are considered to be non-framework Mn(II).