• 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.

• Journal of the Korean Chemical Society
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• v.53 no.4
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• pp.407-414
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• 2009

The solid complexes of Cu(II), Ni(II), Co(II), Mn(II) and Fe(III) with 4-hydroxy-3-(1-{2-(2-hydroxybenzylidene)- amino phenylimino}-ethyl)-6-methy-pyran-2-one (H2L) derived from o-phenylenediamine, 3-acetyl- 6-methyl-(2H) pyran, 2,4 (3H)-dione (dehydroacetic acid or DHA) and salicylic aldehyde have been synthesized and characterized by elemental analysis, conductometry, magnetic susceptibility, UV-visible, IR, $^1H$-NMR spectra, X-ray diffraction, thermal analysis, and screened for antimicrobial activity. The IR spectral data suggest that the ligand behaves as a dibasic tetradentate ligand with ONNO donor atoms sequence towards central metal ion. From the microanalytical data, the stoichiometry of the complexes has been found to be 1:1 (metal: ligand). The physico-chemical data suggests square planar geometry for Cu(II) and Ni(II) complexes and octahedral geometry for Co(II), Mn(II) and Fe(III) complexes. The x-ray differaction data suggests orthorhombic crystal system for Cu(II) complex, monoclinic crystal system for Ni(II), Co(II) and Fe(III) and tetragonal crystal system for Mn(II) complex. Thermal behaviour (TG/DTA) of the complexes was studied and kinetic parameters were determined by Coats-Redfern method. The ligand and their metal complexes were screened for antibacterial activity against Staphylococcus aureus and Escherichia coli and fungicidal activity against Aspergillus Niger and Trichoderma.

• Bulletin of the Korean Chemical Society
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• v.27 no.5
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• pp.687-693
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• 2006

Chromium(III) complexes, cis-[Cr([14]-decane)$(HOC _6H _4COO) _2$]$ClO _4$ I and cis-[Cr([14]-decane)(OH) $(OC _6H _4NO _2)$]$ClO _4{\cdot}H _2O$ II ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) are synthesized and structurally characterized by a combination of elemental analysis, conductivity, IR and VIS spectroscopy, and X-ray crystallography. The complexes crystallizes in the monoclinic space groups, $C2 _1$/a in I and $P2 _1$/n in II. Analysis of the crystal structure of complex I reveals that central chromium(III) ion has a distorted octahedral coordination environment and two hydrogensalicylato ligands are unidentate to the chromium(III) ion via the carboxyl groups in the cis-position. For monomeric complex I the hydrogensalicylato coordination geometry is as follows: Cr-O(average) = 1.984(3) $\AA$;Cr-N range = 2.105(3)-2.141(4) $\AA$;C(24)-O(4) = 1.286(5) $\AA$;N(2)-Cr-N(4) (equatorial position) = 96.97(15)${^{\circ}}$; N(1)-Cr-N(3) (axial position) = 168.27(15)${^{\circ}}$; O(1)-Cr-O(4) = 85.70(13)${^{\circ}}$. The crystal structure of II has indicated that chromium(III) ion is six-coordinated by four secondary amines of the macrocycle, hydroxide anion and nitrophenolate anion.

• Bulletin of the Korean Chemical Society
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• v.25 no.12
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• pp.1757-1763
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• 2004

A new series of nickel(II), cobalt(II)/(III) and copper(II) complexes of 14, 15 and 16-membered of macrocyclic ligands have been prepared and characterized by elemental analyses, IR, UV-VIS and $^1H-NMR$ spectra, magnetic susceptibilities, conductivities, DTA and ESR measurements. Molar conductances in DMF solution indicate that, the complexes are nonelectrolytes except (9-12) complexes. The electronic spectra show that, all complexes are square planar or distorted octahedral geometry. The ESR spectra of solid complexes (4), (8) and (11) show square planar of axial type symmetry $(d_{x2-y2})$ with considerable covalent bond character. However, complex (12) shows a spectrum of octahedral geometry with $d_{z2}$ ground state. Complex (12) shows exploitation in reducing the amount of electron adducts formed in DNA during irradiation with low radiation products.

• Bulletin of the Korean Chemical Society
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• v.18 no.9
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• pp.1022-1028
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• 1997

The reaction between Ni(Ⅱ) and sodium salt of 5,6-dihydro-1,4-dithiin-2,3-dithiolate (DDDT2-) in the presence of oxygen results in the formation of Ni(Ⅲ) species, Ni(DDDT)2-, which is isolated as tetraalkylammonium salt. The same reaction performed in the absence of oxygen yields dianionic Ni(Ⅱ) species, Ni(DDDT)22-, which is also isolated as the tetraethylammonium salt. The bis(5,6-dihydro-1,4-dithiin-2,3-dithiolato) nickelate (Ⅱ) dianion, Ni(DDDT)22-, reacts with methyl iodide to yield unusually stable bis(methylthio)dithiolene complex, Ni(CH3)2C8H8S8. All the isolated dithiolato-nickel(Ⅱ) and nickel(Ⅲ) complexes are characterized by 1H NMR, UV/Vis, IR and mass spectroscopic methods. The internal redox reaction of the nickel(Ⅱ)-dithiolate has been studied by spectro-electrochemical method and the results were compared with those of other metal-dithiolenes. The alkylated nickel(dithiolene) complex presumably undergoes cis-trans isomerization reaction in solution, judging from the experimental results of variable-temperature 1H NMR measurements.

• Bulletin of the Korean Chemical Society
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• v.32 no.3
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• pp.1007-1010
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• 2011

$Ir(dpq/dpqx)_2$(przl-R) complexes were prepared and their electrochemical properties were investigated, where dpq, dpqx and przl-R represent 2,3-diphenylquinoline, 2,3-diphenylquinoxaline and N-phenyl-R-pyrazolonate derivatives, respectively. The iridium complexes containing dpq and dpqx as main ligands were reported to show red phosphorescence, and involvement of a pyrazolonate ancillary ligand in the iridium complexes led to high luminous efficiency for organic light-emitting diodes. In this study, we synthesized red phosphorescent iridium complexes containing a new pyrazolonate ancillary ligand and investigated the HOMOs, LUMOs and resulting electrochemical gaps of $Ir(dpq/dpqx)_2$(przl-R) by cyclic voltammetry. The emission wavelengths of the complexes at 600 - 640 nm were consistent with the gaps of 1.95 - 2.03 eV measured from reduction and oxidation potentials of the complexes.

• Journal of the Korean Chemical Society
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• v.65 no.2
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• pp.93-105
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• 2021

Mononuclear Cu(II), Ni(II), Co(II), Mn(II), Zn(II), Fe(III), Ru(III), and UO2(II) complexes of 2-hydroxy-4-(p-tolyldiazenyl)benzylidene)-2-(p-tolylamino)acetohydrazide (H2L) were prepared by direct method. The ligand and its complexes were isolated in solid state and characterized by analytical techniques such as elemental and thermal analyses, molar conductance, magnetic susceptibility measurements and spectroscopic techniques such as UV-Visible, IR, 1H-NMR and 13C-NMR. The spectral data indicated that the ligand acted as neutral/monobasic bidentate or monobasic/dibasic tridentate ligand bonded to the metal ions through the oxygen atom of ketonic or enolic carbonyl group, azomethine nitrogen atom and deprotonated/protonated phenolic oxygen atom forming either tetragonally distorted octahedral or octahedral. Antimicrobial activities of the ligand and its complexes were evaluated against Escherichia coli, Bacillus subtilis and Aspergillus niger by well diffusion method. The results of antifungal activity showed that the Fe(III) complex (10) exhibited higher antifungal against Aspergillus niger than the other complexes. However, the results of antibacterial activity revealed that Cu(II) complex (4) is the most active against Escherichia coli while the Cu(II) complex (5) and Fe(III) complex (10) exhibited higher antibacterial effect on Bacillus subtilis than the other complexes.

• 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.

• Bulletin of the Korean Chemical Society
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• v.26 no.9
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• pp.1395-1402
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• 2005

The reaction of cis-[Cr([14]-decane)$(OH)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = acetylacetonate (acac), oxalate (ox) or malonate (mal)} leads to a new cis-[Cr([14]-decane)(acac)]$(ClO_4)_2{\cdot}(1/2)H_2O\;(1),\;cis-[Cr([14]-decane)(ox)]ClO_4{\cdot}(1/2)H_2O\;(2)\;or\;cis-[Cr([14]-decane)(mal)]ClO_4{\cdot}(1/4)H_2O\;(3)$. These complexes have been characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. Analysis of the crystal structure of cis-[Cr([14]-decane)(acac)]$(ClO_4)_2{\cdot}(1/2)H_2O$ reveals that central chromium(III) has a distorted octahedral coordination environment and two acetylacetonate-oxygen atoms are bonded to the chromium(III) ion in the cis positions. The angle $N_{axial}-Cr-N_{axial}$ deviates by $11^{\circ}$ from the ideal value of $180^{\circ}$ for a perfect octahedron. The bond angle O-Cr-O between the chromium(III) ion and the two acetylacetonate-oxygen atoms is close to $90^{\circ}$. The bond lengths of Cr-O between the chromium and the acetylacetonate-oxygen atoms are 1.950(3) and 1.954(2) $\AA$. They are shorter than those between chromium and nitrogen atoms of the macrocycle. The IR spectra of 1, 2 and 3 display bands at 1560 {ν (C=O)}, 1710 {${\nu}_{as}$(OCO)} and 1660 $cm^{-1}$ {${\nu}_{as}$(OCO)} attributed to the acac, ox and mal auxiliary ligands stretching vibrations, respectively.

• Bulletin of the Korean Chemical Society
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• v.8 no.3
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• pp.185-189
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• 1987

Reactions of $Ir(ClO)_4(CO)(PPh_3)_2$ with dicyano olefins, cis-NCCH = CH$CH_2$$CH_2$CN (cDC1B), trans-NCCH = CH$CH_2$$CH_2$CN (tDC1B), trans-NC$CH_2$CH = CH$CH_2$CN (tDC2B), and NC$CH_2$$CH_2$$CH_2$$CH_2$CN (DCB) produce binuclear dicationic iridium (I) complexes, $[(CO)(PPh_3)_2Ir-NC-A-CN-Ir(PPh_3)_2(CO)](ClO_4)_2$ (NC-A-CN = cDC1B (1a), tDC1B (1b), tDC2B (1c), DCB (1d)). Complexes 1a-1d react with hydrogen to give binuclear dicationic tetrahydrido iridium (Ⅲ ) complexes, $[(CO)(PPh_3)_2(H)_2Ir-NC-A-CN-Ir(H)_2(PPh_3)_2(CO)](ClO_4)_2$ (NC-A-CN = cDC1B (2a), tDC1B (2b), tDC2B (2c), DCB (2d)). Complexes 2a and 2b catalyze the hydrogenation of cDC1B and tDC1B, respectively to give DCB, while the complex 2c is catalytically active for the isomerization of tDC2B to give cDC1B and tDC1B and the hydrogenation of tDC2B to give DCB at $100^{\circ}C$.