• Bulletin of the Korean Chemical Society
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• v.34 no.1
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• pp.167-173
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• 2013

A series of highly efficient red phosphorescent heteroleptic iridium(III) complexes 1-6 containing two cyclometalating 2-(2,4-substitued phenyl)quinoxaline ligands and one chromophoric ancillary ligand were synthesized: (pqx)$_2Ir$(mprz) (1), (dmpqx)$_2Ir$(mprz) (2), (dfpqx)$_2Ir$(mprz) (3), (pqx)$_2Ir$(prz) (4), (dmpqx)$_2Ir$(prz) (5), (dfpqx)$_2Ir$(prz) (6), where pqx = 2-phenylquinoxaline, dfpqx = 2-(2,4-diflourophenyl)quinoxaline, dmpqx = 2-(2,4-dimethoxyphenyl)quinoxaline, prz = 2-pyrazinecarboxylate and mprz = 5-methyl-2-pyrazinecarboxylate. The absorption, emission, electrochemical and thermal properties of the complexes were evaluated for potential applications to organic light-emitting diodes (OLEDs). The structure of complex 2 was also determined by single-crystal X-ray diffraction analysis. Complex 2 exhibited distorted octahedral geometry around the iridium metal ion, for which 2-(2,4-dimethoxyphenyl)quinoxaline N atoms and C atoms of orthometalated phenyl groups are located at the mutual trans and cis-positions, respectively. The emission spectra of the complexes are governed largely by the nature of the cyclometalating ligand, and the phosphorescent peak wavelengths can be tuned from 588 to 630 nm with high quantum efficiencies of 0.64 to 0.86. Cyclic voltammetry revealed irreversible metal-centered oxidation with potentials in the range of 1.16 to 1.89 V as well as two quasi-reversible reduction waves with potentials ranging from -0.94 to -1.54 V due to the sequential addition of two electrons to the more electron-accepting heterocyclic portion of two distinctive cyclometalated C^N ligands.

• Molecules and Cells
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• v.28 no.5
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• pp.447-453
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• 2009

The quorum sensing (QS) inhibitors that antagonize TraR, a receptor protein for N-3-oxo-octanoyl-L-homoserine lactones (3-oxo-C8-HSL), a QS signal of Agrobacterium tumefaciens were developed. The structural analogues of 3-oxo-C8-HSL were designed by in silico molecular modeling using SYBYL packages, and synthesized by the solid phase organic synthesis (SPOS) method, where the carboxamide bond of 3-oxo-C8-HSL was replaced with a nicotinamide or a sulfonamide bond to make derivatives of N-nicotinyl-L-homoserine lactones or N-sulfonyl-L-homoserine lactones. The in vivo inhibitory activities of these compounds against QS signaling were assayed using reporter systems and compared with the estimated binding energies from the modeling study. This comparison showed fairly good correlation, suggesting that the in silico interpretation of ligand-receptor structures can be a valuable tool for the pre-design of better competitive inhibitors. In addition, these inhibitors also showed anti-biofilm activities against Pseudomonas aeruginosa.

• Journal of the Korean Applied Science and Technology
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• v.19 no.2
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• pp.103-107
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• 2002

Diphosphine dinuclear gold(I) complexes were synthesized from the reaction of bridged diphosphines and gold ions. As a bridged diphosphine, 1,2-bis(diphenylphosphino)metbane (dppm) or 1,1'-Bis(diphenylphosphino) ferrocene (dppf) was introduced. As anionic ligands, CI was first coordinated to Au, resulting in (diphosphine)$(AuCl)_{2}$. Then, the ligand, SPh, was substituted for Cl in the chloride complex to give (diphosphine)$(AuSPh)_{2}$. As a result, three digold complexes, (dppm)$(AuCl)_{2}$. (I), (dppf)$(AuCl)_{2}$. (II), and (dppf)$(AuSPh_{2}$. (III) were prepared in this study. The thermal properties were investigated at first hand to confirm that the gold complexes were in fact formed. The digold complexes were decomposed above $200^{\circ}C$ while the ligand, dppm or dppf, melts under $180^{\circ}C$ The photoluminescence (PL) spectra of the spin-coated thin films showed the maximum peak at 590, 595, and 540nm for the complex, I, II, and III, respectively. These complexes were found to give the orange color phosphorescence. Therefore, these digold complexes can be candidates for orange-red phosphorescent materials in organic electroluminescent devices (OELD). Further studies on application of the complexes as a dopant in an emitting layer are in progress in our laboratory.

• Journal of the Korean Chemical Society
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• v.36 no.4
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• pp.546-551
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• 1992

Reaction mechanism on the solvent extraction of nickel(Ⅱ) with N-benzylisonitrosoacetylacetone imine(HIAANB) was studied spectrophotometrically. Absorbance was measured by changing the ligand HIAANB concentration in the chloroform organic phase and the pH values in the agueous solution phase. From the absorbance data, the reaction rate was found to be the first order for HIAANB concentration and the inverse first one for [$H^+$]. The rate determining step of the extraction reaction and the rate equation are as follows; $Ni^{2+}$＋HIAANB ${\to}$ Ni-IAANB$^+$＋$H^+$ -d[Ni$^{2+}$] / dt = K'[Ni$^{2+}$][HIAANB]$_0$ / [H$^+$] Calibration curve for the spectrophotometric determination of nickel(Ⅱ) ion in the aqueous solution was linear below the concentration of 1.17 ppm at the optimum experimental condition. And the ligand-to-metal ratio, the relationship between extractability and pH of the aqueous phase, and the effect of diverse ion on the determination of nickel(Ⅱ) ion were examined.

• The Transactions of the Korean Institute of Electrical Engineers C
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• v.48 no.5
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• pp.285-295
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• 1999

Electroluminescent(EL) devices based on organic materials have been of great interest due to their possible applications for large-area flat-panel displays. They are attractive because of their capability of multi-color emission, and low operation voltage. An approach to realize such device characteristics is to use active layers of lanthanide complexes with their inherent extremely sharp emission bands in stead of commonly known organic dyes. In general, organic molecular compounds show emission due to their $\pi$-$\pi*$ transitions resulting in luminescence bandwidths of about 80 to 100nm. Spin statistic estimations lead to an internal quantum efficiency of dye-based EL devices limited to 25%. On the contrary, the fluorescence of lanthanide complexes is based on an intramolecular energy transfer from the triplet of the organic ligand to the 4f energy states of the ion. Therefore, theoretical internal quantum efficiency is principally not limited. In this study, Powders of TPD, $Eu(TTA)_3(phen) and AlQ_3$ in a boat were subsequently heated to their sublimation temperatures to obtain the growth rates of 0.2~0.3nm/s. Organic electrolumnescent devices(OELD) with a structure of $glass substrate/ITO/Eu(TTA)_3(phen)/AI, glass substrate/ITO/TPD/Eu(TTA)_3(phen)/AI and glass substrate/ITO/TPD/Eu(TTA)_3(phen)/AIQ_3AI$ structures were fabricated by vacuum evaporation method, where aromatic diamine(TPD) was used as a hole transporting material, $Eu(TTA)_3(phen)$ as an emitting material, and Tris(8-hydroxyquinoline)Aluminum$(AlQ_3)$ as an electron transporting layer. Electroluminescent(EL) and current density-voltage(J-V) characteristics of these OELDs with various thickness of $Eu(TTA)_3(phen)$ layer were investigated. The triple-layer structure devices show the red EL spectrum at the wavelength of 613nm, which is almost the same as the photoluminescent(PL) spectrum of $Eu(TTA)_3(phen)$.It was found from the J-V characteristics of these devices that the current density is not dependent on the applied field, but on the electric field.

• Applied Chemistry for Engineering
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• v.33 no.3
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• pp.296-301
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• 2022

Due to the fact that zirconium based metal-organic frameworks (Zr-MOFs), such as UiO-66, have a large specific surface area and excellent selective adsorption capacity, Zr-MOFs are gaining attention as materials that can provide protection from the attack of chemical warfare agents in battleground. However, most of the metal-organic frameworks have an issue of selective adsorption capacity degraded by water molecules when exposed to the atmosphere, because of the weak metal-organic ligand bonds and the presence of voids. Therefore, polydimethylsiloxane (PDMS), a representative hydrophobic polymer material, was coated on the surface of UiO-66 to enhance the sustainability of the diisopropyl methylphosphonate (DIMP) sorption capacity in the battleground condition. Through the analysis of surface structure and organic functional group distribution of PDMS coated UiO-66, silicon was confirmed to be evenly coated. The contact angle increased by over 30° for the PDMS coated UiO-66, indicating that the hydrophobicity was improved. In addition, both the UiO-66 and PDMS coated UiO-66 were used as adsorbents for DIMP, a similar chemical warfare agent, to investigate the durability of adsorption capacity in a high humidity environment. The PDMS coated UiO-66 showed higher durability of adsorption capacity for 20 days than that of pristine UiO-66.

• Korean Journal of Materials Research
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• v.11 no.1
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• pp.20-26
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• 2001

The deposition characteristics of MOCVO Cu using the (hfac)Cu(I) (1,5-DMCOD)(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato Cu(I) 1,5-dimethyl-cyclooctadine) as a precursor have been investigated in terms of the effects of hydrogen and H(hfac) ligand addition with He carrier gas. MOCVD Cu using a Helium carrier gas showed a low deposition rate (20~$125{\AA}/min$) at the substrate temperature range of 180~$230^{\circ}C$. Moreover, the Cu film deposited at 19$0^{\circ}C$ was very thin (~$700{\AA}$) and showed the lowest resistivity value of $2.8{\mu}{\Omega}-cm$. The deposition rate of MOCVD Cu using $H_2$or H(hfac) addition was significantly enhanced especially at the low temperature region (180~$190^{\circ}C$). Furthermore, thinner Cu films (~$500{\AA}$) provided low resistivity (3.6~$2.86{\mu}{\Omega}-cm$). From surface reflectance measurement, very thin films deposited by using different gas system revealed good surface morphology comparable with sputtered Cu film ($300^{\circ}C$, vacuum-anneal). Hence, Cu film using (hfac)Cu(1,5-DMCOD) as a precursor is expected as a good seed layer in the electrochemical deposition process for Cu metallization.

• Molecular & Cellular Toxicology
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• v.4 no.3
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• pp.183-191
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• 2008

Volatile organic compounds (VOCs) are common constituents of cleaning and degreasing agents, paints, pesticides, personal care products, gasoline and solvents. And VOCs are evaporated at room temperature and most of them exhibit acute and chronic toxicity to human. Benzene is the most widely used prototypical VOC and the toxic mechanisms of them are still unclear. The multi-step process of toxic mechanism can be more fully understood by characterizing gene expression changes induced in cells by toxicants. In this study, DNA microarray was used to monitor the expression levels of genes in HepG2 cells and HL-60 cells exposed to the benzene on IC20 and IC50 dose respectively. In the clustering analysis of gene expression profiles, although clusters of HepG2 and HL-60 cells by benzene were divided differently, expression pattern of many genes observed similarly. We identified 916 up-regulated genes and 1,144 down-regulated genes in HepG2 cells and also 1,002 up-regulated genes and 919 down-regulated genes in HL-60 cells. The gene ontology analysis on genes expressed by benzene in HepG2 and HL-60 cells, respectively, was performed. Thus, we found some principal pathways, such as, focal adhesion, gap junction and signaling pathway in HepG2 cells and toll-like receptor signaling pathway, MAPK signaling pathway, p53 signaling pathway and neuroactive ligand-receptor interaction in HL-60 cells. And we also found 16 up-regulated and 14 down-regulated commonly expressed total 30 genes that belong in the same biological process like inflammatory response, cell cycle arrest, cell migration, transmission of nerve impulse and cell motility in two cell lines. In conclusion, we suggest that this study is meaningful because these genes regarded as strong potential biomarkers of benzene independent of cell type.

• Journal of the Korean Vacuum Society
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• v.15 no.5
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• pp.485-492
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• 2006

Two new copper(I) complexes with organic ligands, $[Cu^I(hfac)]_2(DVTMSO)$ and $[Cu^I(hfac)]_2(HD)$ (hfac=hexafluoroacetylacetonate, DVTMSO=1,2-divinylte-tramethyl-disiloxane, HD=1,5-hexadiene) were synthesized and used for copper metal-organic chemical vapor deposition. In these compounds, two Cu(hfac) fragments are bonded by one neutral ligand forming unusual structure with respect to other Cu(I) complexes. The compounds exhibited relatively high volatility and stability when compared to other copper(I) precursors. By using the reported compounds as precursors, a continuous Cu layer was not formed but the Cu islands were only observed. And the shape and size of Cu islands are significantly changed as a function of the substrate temperature.

• Bulletin of the Korean Chemical Society
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• v.27 no.11
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• pp.1757-1762
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• 2006

A solvent sublation using salphen as a ligand was studied and applied for the determination of trace Ni(II), Co(II) and Cu(II) in water samples. The fundamental study was investigated by a solvent extraction process because the solvent sublation was done by extracting the floated analytes into an organic solvent from the aqueous solution. The salphen complexes of Ni(II), Co(II) and Cu(II) ions were formed in an alkaline solution of more than pH 8 and then they were extracted into m-xylene. It was known that the each metallic ion formed 1 : 1 complex with the salphen and the logarithmic values of extraction constants for the complexes were 3.3 5.1 as an average value. Based on the preliminary study, the procedure was fixed for the separation and concentration of the analytes in samples. Various conditions such as the pH of solutions, the influence of $NaClO_4$, the bubbling rate and time of $N_2$ gas, and the type of organic solvent were optimized. The metal-salphen complexes could be extracted into m-xylene from the solution of more than pH 8, but the pH could be shifted to acidic solution of pH 6 by the addition of $NaClO_4$. In addition, the solvent sublation efficiency of the analytes was increased by adding $NaClO_4$. The recovery of 97-115% was obtained in the spiked samples in which given amounts of 0.3 mg/L Ni(II), 0.8 mg/L Co(II) and 0.04 mg/L Cu(II) were added.