• Title/Summary/Keyword: Coordinating ligands

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ZnO Nanoparticles with Hexagonal Cone, Hexagonal Plate, and Rod Shapes: Synthesis and Characterization

  • Kim, Sun-Young;Lee, In-Su;Yeon, Yun-Seon;Park, Seung-Min;Song, Jae-Kyu
    • Bulletin of the Korean Chemical Society
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    • v.29 no.10
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    • pp.1960-1964
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    • 2008
  • The roles of coordinating ligands (TOPO, OA, HDA, and TDPA) for the synthesis of ZnO nanoparticles are investigated. Various shapes (hexagonal cone, hexagonal plate, and rod) and sizes (5-100 nm) of ZnO nanoparticles are prepared in relation to the coordinating ligands. The hexagonal shapes ($\leq$ 100 nm) are synthesized with TOPO and OA, while smaller size nanorods (5 ${\times}$ 30 nm) are with TOPO and TDPA. The relative intensities of two distinctive emission bands centered at 385 and 500 nm, which are related to the exciton and defect states, respectively, depend on the crystal qualities of ZnO nanoparticles affected by the coordinating ligands. The intense UV emissions with the reduced visible emissions are found in the monodisperse nanoparticles such as hexagonal cones and nanorods, suggesting that the monodispersity as well as the crystallinity is closely related to the coordinating ligands. The blue-shift of photoluminescence and absorption edge is observed in the nanorods, because the sizes of the nanorods are in the quantum confinement regime.

Synthesis, Antioxidant Activity and Fluorescence Properties of Novel Europium Complexes with (E)-2- or 4-hydroxy-N'-[(2-hydroxynaphthalen-1-yl)methylene]benzohydrazide Schiff Base

  • Liu, Lijun;Alam, Mohammad Sayed;Lee, Dong-Ung
    • Bulletin of the Korean Chemical Society
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    • v.33 no.10
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    • pp.3361-3367
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    • 2012
  • Two novel Eu(III) complexes with notable properties have been successfully prepared with hydrazone Schiff base ligands, (E)-2-hydroxy-N'-[(2-hydroxynaphthalen-1-yl)methylene]benzohydrazide (3a) and (E)-4-hydroxy-N'-[(2-hydroxynaphthalen-1-yl)methylene]benzohydrazide (3b). DFT, FMO energy and Mulliken charge distribution studies of the ligands allowed us to hypothesize that their HC=N, > C=O and -OH (naphthyl) groups were involved in coordinating with the $Eu^{3+}$ ion. The eight coordination sites of the $Eu^{3+}$ ion were occupied by the three functional groups of the two ligands (3a or 3b) mentioned above and two water molecules. Similar UV, IR and fluorescence spectra indicated the presence of comparable coordination environments for the $Eu^{3+}$ ion in both complexes. Both the ligands and their complexes exhibited moderate DPPH radical scavenging activity. Moreover, it was found that the Eu(III) complexes exhibited fluorescence properties.

Delicate Difference in Coordinating Nature between Copper(II) and Nickel(II) Ions. Structural Properties of Copper(II) and Nickel(II) Nitrate Containing 1,2-Bis(dimethyl-3-pyridylsilyl)ethane

  • Kim, Shin-A;Kim, Chi-Won;Noh, Tae-Hwan;Lee, Young-A;Jung, Ok-Sang
    • Bulletin of the Korean Chemical Society
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    • v.31 no.8
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    • pp.2158-2162
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    • 2010
  • Studies on the molecular construction and structures of $M(NO_3)_2$ (M = Cu(II), Ni(II)) complexes with 1,2-bis(dimethyl-3-pyridylsilyl)ethane (L) have been carried out. Formation of each molecular skeleton appears to be primarily associated with a suitable combination of bidentate N-donors of L and coordinating nature of octahedral metal(II) ions: [$Cu(NO_3)_2(L)_2$] yields a 2-dimensional sheet structure consisting of 44-membered $Cu_4L_4$ skeleton whereas $[Ni(L)_2(H_2O)_2](NO_3)_2$ produces an interpenetrated 3-dimensional structure consisting of 66-membered cyclohexanoid ($M_6L_6$) skeleton. The Cu(II) ion prefers nitrate whereas the Ni(II) ion prefers water molecules as the fifth and the sixth ligands.

Enantioselective Hydrosilylation of Imines Catalyzed by Diamine-Zinc Complexes

  • Park, Bu-Mahn;Feng, Xinhui;Yun, Jae-Sook
    • Bulletin of the Korean Chemical Society
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    • v.32 no.spc8
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    • pp.2960-2964
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    • 2011
  • The efficient asymmetric hydrosilylation of imines in the presence of polymethylhydrosiloxane has been investigated by screening chiral diamine-zinc complexes. A series of chiral diamine ligands were prepared from optically pure 1,2-diphenyl-1,2-ethanediamine and screened for effectiveness. N-Benzylic substituents were required for high enantioselectivity; ligands with bulky groups or extra coordinating groups such as OH and S lowered the catalytic activity. The level of asymmetric induction was usually in >90% ee range for aromatic imine substrates. A linear correlation between the ee of the ligand and that of the product was observed, indicating the presence of a 1:1 ratio of ligand to metal coordination in the active catalytic complex.

Synthesis and Characterization of Phthalocyaninatometal (PcM, M=$Fe^{2+}$, $Co^{2+}$ Complexes with Monodenate Aromatic Isocyanide Ligands

  • 임윤묵;박하선;송수호;박찬조;유하일;이종기;양현수
    • Bulletin of the Korean Chemical Society
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    • v.20 no.6
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    • pp.701-704
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    • 1999
  • Metallophthalocyanines [PcM, Pc: phthalocyanine, M: Fe 2+ , Co 2+ ] were reacted with α-isocyanonaphthalene( α-in) and α-isocyanoanthracene (α-ia) to form monomeric complexes. The synthesis and coordination behaviour of the isocyanides as a ligand (L) are discussed. All the products were characterized by spectroscopic methods and instrumental analysis. The electrical conductivities of these complexes, which were not treated with dopant, were attributed to the metal-ligand electron delocalization in the PcML2 complexes. The complexes have an enlarged macrocycle where the π-electron back donating ability of PcM is stronger than the σ-electron coordinating ability of the isonitrile ligands. Their electrical conductivities were measured as σRT = 2.1×10 -9 ~3×10 -10 S/cm. Also thermal stability was investigated in this study.

A Study on Synthesis and Characterization of Dinitrosylmolybdenum Complexes (디니트로실 몰리브덴 착물의 합성과 특성에 관한 연구)

  • Doh, Kiel Myung;Kim, Ill Chool;Choi, Bo Yong
    • Journal of the Korean Chemical Society
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    • v.39 no.3
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    • pp.191-197
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    • 1995
  • The reactions of [${Mo(NO)_2Cl_2}_n$] with unidentate ligands in $CH_2Cl_2$ solvent afforded monomeric complexes [$Mo(NO)_2L_2Cl_2$]. $[Mo(NO)_2L_4](ClO_4)_2$ was obtained by reaction of unidentate with $[Mo(NO)_2L_2Cl_2]$ in aceton solvent. 4-Dimethylaminopyridine(dmap), pyridine(py), and isoquinoline(isoq) were used as coordinating ligands. These dinitrosylmolybdenum complexes are prepared and characterized by elemental analysis, $^1H$ NMR, infrared, and UV-Visible spectroscopy. The infrared spectra indicate that the NO groups occupy cis-positions of the octahedral.

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Metal-Nitrosyl Complexes (I) Synthesis and Characterization of Dinitrosylmolybdenum (O) Complexes (금속-니트로실 착물 (제 1 보) 디니트로실몰리브덴(O) 착물의 합성과 특성)

  • Oh Sang-Oh;Mo Seong-Jong
    • Journal of the Korean Chemical Society
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    • v.36 no.5
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    • pp.661-668
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    • 1992
  • The polymeric compound [{Mo(NO)_2Cl_2}n] was prepared by reductive nitrosylation of NaNO_2 and acidified FeSO_4 with MoCl_5. The reactions of [{Mo(NO)_2Cl_2}n] with unidentate and bidentate ligands afforded neutral monomeric $[Mo(NO)_2Cl_2L_2(or L-L)] in high yield (80∼90%). 3,5-Lutidine, {\gamma}-Cyanopyridine, 1,2-Phenylenediamine, 1,10-Phenanthroline, sym-Diphenylethylenediamine, 9,10-Phenanthrenequinone, 1,3-Bis(diphenylphosphino)propane and 8-Hydroxyquinoline were used as coordinating ligands. The preparation and characterization of these dinitrosylmolybdenum complexes by elemental analysis, 1H NMR, infrared, and UV-Visible spectroscopy are reported. The infrared spectra indicate that in all of the compounds prepared, the NO groups occupy cis-positions in the octahedral group of ligands.

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Syntheses and Properties of New Nickel(II) Complexes of 14-Membered Pentaaza Macrocyclic Ligands with C-Nitro and N-Alkyl Pendant Arms

  • Kang, Shin-Geol;Choi, Jang-Sik
    • Bulletin of the Korean Chemical Society
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    • v.15 no.5
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    • pp.374-378
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    • 1994
  • Square planar nickel(II) complexes with various 1-alkyl derivatives of the 14-membered pentaaza macrocycle 8-methyl-8-nitro-1,3,6,10,13-pentaazacyclotetradecane can be readily prepared by two-step metal template condensation reactions of ethylenediamine, nitroethane, formaldehyde, and appropriate primary alkylamines. In coordinating solvents the nickel (II) complexes form octahedral species containing two axially coordinated solvent molecules and thus show square planar-octahedral equilibrium. The properties of the pentaaza macrocyclic complexes are considerably different from those of the complexes of analogous hexaaza and tetraaza macrocyclic complexes. Synthesis, characterization, and spectroscopic and chemical properties of the new complexes are described.

Template Synthesis of New Nickel(Ⅱ) Comlexes of 14-Membered Pentaaza Macrocyclic Ligands: Effects of C-Alkyl and N-Hydroxyalkyl Pendant Arms on the Solution Behaviors of the Complexes

  • 강신걸;최장식;김성진
    • Bulletin of the Korean Chemical Society
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    • v.16 no.6
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    • pp.518-523
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    • 1995
  • New square planar nickel(Ⅱ) complexes with various 1-alkyl (4a-4c) and 1-hydroxyalkyl (4d-4f) derivatives of the 14-membered pentaaza macrocycle 8-ethyl-8-nitro-1,3,6,10,13-pentaazacyclotetradecane have been synthesized by two-step metal template condensation reactions of ethylenediamine, nitroethane, formaldehyde, and appropriate primary amines. The nitro group and/or hydroxyl group of 4a-4f are not directly involved in the coordination. The nickel(Ⅱ) complexes exist in coordinating solvents such as MeCN, Me2SO, and H2O as equilibrium mixtures of the square planar [Ni(L)]2+(L=4a-4f) and octahedral species [Ni(L)S2]2+(S=solvent molecule). Although the ligand field strength and redox potentials of the complexes are not affected by the nature of the substituents, the formation of octahedral species for 4d-4f in MeCN is strongly restricted by the hydroxyl group. Synthesis, characterization, and solution behaviors of the nickel(Ⅱ) complexes are described.