• Bulletin of the Korean Chemical Society
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• v.30 no.5
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• pp.1157-1163
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• 2009

Complexes of Pd(btnbmtp)$Cl_2$ and Pt(btnbmptp)$Cl_2$ (btnbmtp = 2,5-bis(thiophen)-1-nonyl-3,4-bis(methylthio)- pyrrole) were prepared and their crystal structures were determined at room temperature. In the structures, the two thiophene moieties lie in cis form with an average dihedral angle of $55.26^{\circ}$ to the pyrrole frame. The luminescence properties of the free ligand and the complexes were investigated in solution and solid states. The luminescence of the compounds were not favored by substituting thiophene moieties to the pyrrole frame, compared to the unsubstituted nbmptp (nbmptp = 1-nonyl-3,4-bis(methylthio)pyrrole). In particular, thiophene substitution quenched the emission from the complexes dissolved in ,$CH_2Cl_2$ and reduced the charge transfer transitions from S atoms of the thio moieties to Pt in crystalline state, which was very characteristic of Pt(nbmptp)$Cl_2$.

• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.2056-2062
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• 2013

The dihydroxy naphthalene/$TiO_2$ complexes with different substitution patterns were prepared by surface modification. X-ray diffraction, UV-Vis spectroscopy, photoluminescence, and X-ray photoelectron spectroscopy were used to characterize the prepared composite materials. The results indicated that the surface modification did not influence the crystallization of $TiO_2$. The visible-light absorbances of prepared dihydroxy naphthalene/$TiO_2$ complexes could be assigned to the ligand-to-metal charge transfer. The obtained catalyst exhibited outstanding photocatalytic activity and stability under visible light. A linear relationship existed between the percentages of hydroxynaphthalenes coordinated on $TiO_2$ surface and $H_2$ production ability. The substitution pattern of dihydroxy naphthalene and $CH_3OH$ content could also influence the photocatalytic performance remarkably. The photocatalytic $H_2$ production ability was further improved after loading with ultra low concentration of Pt, 0.02 wt %. The possible mechanism was proposed.

• Journal of the Korean Chemical Society
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• v.30 no.5
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• pp.441-448
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• 1986

Dioxobis(sub.-salicylaldiminato) molybdenum (VI) complexes, $MoO_2\;(X-sal-N-R)_2,\;(X=H,\;5-CH_3,\;R=C_6H_5,\;p-F-C_6H_4,\;m-Cl-C_6H_4,p-I-C_6H_4\;and\;p-C_2H_5-C_6H_4)$, have been prepared by reactions of dioxobis(sub.-salicylaldehydato) molybdenum (VI), $MoO_2(X-sal)_2$ with primary amines, in which $MoO_2(X-sal)_2$ complexes were obtained by acidification of a mixture solution of ammonium paramolybdate in water and appropriate salicylaldehyde in methanol. All these complexes show two strong Mo=O stretching imodes in the 900-940$cm^{-1}$ and p.m.r. spectra exhibited only one signal for the azomethine group. These results confirmed that the complexes are six-coordinated octahedron with a $cis-MoO_2$ group and the geometrical configurations of the complexes possess a C2 axis of symmetry. From the mass analyses of the complexes, it found that the composition ratios of $MoO_2$ : ligand are 1 : 2. The charge transfer transition corresponding to N-Mo, and O-Mo occured at 29,000$cm^{-1}$ and 32,000$cm^{-1}$ respectively. Where, the complexes were found to be non-ionic materials by conductivity measurements in dimethylformamide.

• Journal of Environmental Science International
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• v.1 no.1
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• pp.69-76
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• 1992

The effects of $Ca_{2+}$ ion on the formation of micelle colloid of nonionic surfactants, nonylphenol-(ethylene oxide)n [NP-(EO)n: n= 11, 40, 100) were investigated by the iodine solubilization method. The characteristics of spectra depended on the concentration of $Ca_{2+}$ ion and the number of EO unit. Above CMC(critical micelle concentration), the intensity of the CT (charge transfer) band by the addition of $Ca_{2+}$ ion for the NP-(EO)11 and NP-(EO)40 increased and when decreased and for the NP-(EO)In continuously increased. The increase in the intensity of CT band were attributed to the compactness of micelle in the presence of $Ca_{2+}$ ion. These phenomena may be explained by the fact that the linear ethylene oxide (EO) chain, relatively free to assume various configuration in aqueous solution, could form a pseudo-crown ether structures capable of forming complexes with $Ca_{2+}$ ion.

• Bulletin of the Korean Chemical Society
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• v.21 no.8
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• pp.823-827
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• 2000

Gas-Phase reactions of methyl and ethyl nitrites with anionic nucleophiles of SH-, F- and OH- are investigated theoretically at the MP2/6-311+G* level. The SN2 processes are all highly exothermic and proceed with a typ-icaI double-weIl reaction coordinate profile. The elimination reactions of methyl nitrite with SH- and F- are double-well energy surface processes,with stabilizedproduct complexes of NO-...H2S and NO-...HF, pro-ceeding by an E1 cb-like E2 mechanism. The $\beta-elimination$ of ethyl nitrite is an E2 type process. The $\alpha-elimi-nation$ reactions of methyl and ethyl nitrites with OH- have triple-well energy profiles of Elcb pathway with an $\alpha-carbanion$ intermediate which is stabilized bythe vicinal $nc\alpha-{\sigma}*o-N$ charge transfer interactions. CompIex-ation ofmethyl carbanion with HF seems to provide a stable intermediate within a triple-well energy profile of El cb channel in the reaction of F- with methyl nitrite.

• Applied Chemistry for Engineering
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• v.29 no.5
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• pp.519-523
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• 2018

Cyclodextrins are a class of oligosaccharides having an extremely low toxicity, so that they have been used for the formation of host-guest complexes and removal of toxic gases or molecules. In this study, the subtle phenomenon associated with the formation of host-guest complexes between cyclodextrin and toxic molecules (methyl paraben) was experimentally investigated. First, the formation of cyclodextrin-methyl paraben complexes was monitored by UV/Vis spectroscopy as a function of the cyclodextrin concentration. Secondly, the electrochemical measurement was performed with the surface engineered Au electrode having cyclodextrin molecules on the Au substrate. The sensing signal derived from the addition of methyl paraben solution into the Au surface was measured delicately. This study can be informative for future applications such as sensors.

• Bulletin of the Korean Chemical Society
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• v.29 no.3
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• pp.599-603
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• 2008

The complexes Pd(nbmtp)Cl2 and Pt(nbmtp)Cl2 (nbmptp = 1-nonyl-3,4-bis(methylthio)pyrrole) were prepared and their x-ray structures were determined at room temperature. The four-coordinated metal unit and the pyrrole ring formed a nearly planar geometry. The free ligand dissolved in CH2Cl2 produced two luminescence bands associated with the lone-pair electron of S (l max = 525 nm) and the pyrrole p electron (l max = 388 nm). When the two complexes were dissolved in CH2Cl2, these two luminescence bands were also observed, although the low-energy band was blueshifted. For the crystalline Pt(II) complex, only the strong charge transfer band (l max = 618 nm) from the d* orbital of Pt resulted from excitation of the lone-pair electron of S.

• Bulletin of the Korean Chemical Society
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• v.33 no.12
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• pp.4084-4092
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• 2012

Theoretical calculations based on density functional theory (DFT) were performed to study the substituent effect on the geometric and electronic structures as well as the biological behavior of technetium-99m-labeled diphosphonate complexes. Optimized structures of these complexes are surrounded by six ligands in an octahedral environment with three unpaired 4d electrons ($d^3$ state) and the optimized geometry of $^{99m}Tc$-MDP agrees with experimental data. With the increase of electron-donating substituent or tether between phosphate groups, the energy gap between frontier orbitals increases and the probability of non-radiative deactivation via d-d electron transfer decreases. The charge distribution reflects a significant ligand-to-metal electron donation. Based on the calculated geometric and electronic structures and biologic properties of $^{99m}Tc$-diphosphonate complexes, several structure-activity relationships (SARs) were established. These results may be instructive for the design and synthesis of novel $^{99m}Tc$-diphosphonate bone imaging agent and other $^{99m}Tc$-based radiopharmaceuticals.

• Journal of the Korean Chemical Society
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• v.36 no.5
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• pp.621-626
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• 1992

The effects of $Ca^{2+}$ ion on the charge transfer(CT) interaction of $4-(C_9H_{19})C_6H_4O(CH_2CH_2O)_{40} [NP-(EO)_{40}]$ with iodine in aqueous solution were investigated by UV-visible spectrophotometer. Maximum absorption wavelengths to the CT interaction were in the vicinity of 390 nm, and by the addition of $Ca^{2+}$ ion shifted toward 370 nm. Above CMC, the intensity of the CT interaction by the addition of $Ca^{2+}$ ion were increased and then decreased. The increase in the intensity of CT band were attributed to the increase of the donor-acceptor overlap with iodine caused by the compactness of micelle in the presence of $Ca^{2+}$ ion. These phenomena suggest that the linear oxyethylene(EO) chains, relatively free to assume various configuration in aqueous solution, could form a pseudo-crown ether structures capable of forming complexes with $Ca^{2+}$ ion.

• Journal of the Korean Chemical Society
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• v.37 no.1
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• pp.36-42
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• 1993

In the presence of $Ca^{2+}$ ion, the charge transfer (CT) interaction of nonionic surfactants, $nonylphenol-(ethylene oxide)_n\;[NP-(EO)_n; n = 11, 40, 100]$ with iodine in aqueous solution were investigated by UV-visible spectrophotometer. The characteristics of spectra depended on the concentration of $Ca^{2+}$ ion and the number of EO unit. Above CMC, the intensity of the CT band by the addition of $Ca^{2+}$ ion for the $NP-(EO)_{11}$ and $NP-(EO)_{40}$ increased and then decreased, while for the $NP-(EO)_{100}$ continuously increased. The increase in the intensity of CT band were attributed to the compactness of micelle in the presence of $Ca^{2+}$ ion. These phenomena may be explained by the fact that the linear ethylene oxide (EO) chain, to be free configuration in aqueous solution, could form a pseudo-crown ether structures capable of forming complexes with $Ca^{2+}$ ion.