• Title/Summary/Keyword: 1,10-Phenanthroline Ligands

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Structure of Chloro bis(1,10-phenanthroline)Cobalt(II) Complex, [Co(phen)2(Cl)(H2O)]Cl·2H2O

  • Pu Su Zhao;Lu De Lu;Fang Fang Jian
    • Journal of the Korean Chemical Society
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    • v.47 no.4
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    • pp.334-338
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    • 2003
  • The crystal structure of $[Co(phen)_2(Cl)(H_2O)] Clㆍ2H_2O$(phen=1,10-phenanthroline) has been determined by X-ray crystallography. It crystallizes in the triclinic system, space group P1, with lattice parameters a=9.662(2), b=11.445(1), c=13.037(2)${\AA}$ ${\alpha}$=64.02(1), ${\beta}$=86.364(9), ${\gamma}=78.58(2)^°$, and Z=2. The coordinated cations contain a six-coordinated cobalt atom chelated by two phen ligands and one chloride anion and one water ligand in cis arrangement. In addition to the chloride coordinated to the cobalt, there are one chloride ion and four water molecules which complete the crystal structure. In the solid state, the title compound forms three dimensional network structure through hydrogen bonds, within which exists the strongest hydrogen bond (O(3)-O(4)=2.33${\AA}$). The intermolecular hydrogen bonds connect the $[Co(phen)_2(Cl)(H_2O)]1+,\;H_2O$ moieties and chloride ion.

Bistability of $Co^{III}$(N-N)(3,6-DBSQ)(3,6-DBCat):Subtle Diimine Ligand Effect (N-N=4,7-Dimethyl-1,10-phenanthroline, 5-Chloro-1,10-phenanthroline;DBSQ=Di-tert-butylsemiquinonato;DBCat=Di-tert-butylcatecholato)

  • Ok-Sang Jung;Young-A Lee;Younkyoo Kim;Youn Soo Sohn
    • Bulletin of the Korean Chemical Society
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    • v.15 no.8
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    • pp.641-643
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    • 1994
  • Studies of Co(N-N)(3,6-DBSQ)(3,6-DBCat)(N-N=4,7-dimethyl-1 ,10-phenanthroline, 5-chloro-1,10-phenanthroline; DBSQ=di-tert-butylsemiquinonato; DBCat=di-tert-butylcatecholato) have been carried out on the bistability by intramolecular cobalt-quinone electron transfer in solid state. The title complexes dominantly exist as $Co^{III}$(N-N)(3,6-DBSQ)(3,6-DBCat) at room temperature and display a significant bistability on temperature variation. Subtle change in optical spectra and magnetic properties is observed when diimine ligands are changed.

Dimeric Silver(I) Complex: Bis(dipropyldithiophosphato) bis(1,10-phenanthroline) Disilver(I); Dimeric Silver(I) Complex: Bis(dipropyldithiophosphato) bis(1,10-phenanthroline) Disilver(I);Ag2[Phen]2[S2P(OPr)2]2 (은(I)화합물:비스(디프로필디싸이오포스페이토)비스(1,10-펜안트로린)이온(I);Ag2[Phen]2[S2P(OPr)2]2)

  • Fang Fang Jian;Hai Lian Xiao;Huan Xiang Wang;Kui Jiao
    • Journal of the Korean Chemical Society
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    • v.47 no.1
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    • pp.26-30
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    • 2003
  • The dinuclear $Ag_2[Phen]_2[S_2P(OPr)_2]_2$(phen=1,10-phenanthroline; Pr=propyl), was prepared by the reaction of bis(dipropyldithiophosphato) silver(I) complex with 1,10-phenanthroline ligand, and its structure was determined by X-ray crystallography. The two dipropyldithiophosphato ligands each bridge two silver atoms to form an eight-membered $Ag_2S_4P_2$ ring, while the 1,10-phenanthroline molecule coordinates to a silver atom to complete the local tetrahedral geometry for the metal ion. The Ag-S bond distances are 2.559(1) and 2.567(1)${\AA}$, and the Ag-N bond distances are 2.366(3) and 2.471(3)${\AA}$.

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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Luminescence and Crystal-Field Analysis of Europium and Terbium Complexes with Oxydiacetate and 1,10-Phenanthroline

  • Kang, Jun-Gill;Kim, Tack-Jin
    • Bulletin of the Korean Chemical Society
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    • v.26 no.7
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    • pp.1057-1064
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    • 2005
  • Photoluminescence (PL) spectra of Eu(III) and Tb(III) complexes with mixed oxydiacetate (ODA) and 1,10-phenanthroline (phen) ligands and with homoleptic ODA reveal characteristic line-splitting at 10 K, depending on the site-symmetry of the lanthanide ion in the complex. The energy-level schemes of the $^7F_J$ states and the emitting levels for Eu(III) and Tb(III) ions have been proposed by simulating the line splitting in the framework of crystal-field Hamiltonian. The sets of refined crystal-field parameters for the experimentally determined sitesymmetry satisfactorily reproduce the experimental energy-level schemes. In addition, the PL quantum yield and the decay time were determined at room temperature. The PL quantum yields of [$Eu(ODA){\cdot}(phen){\cdot}4H_2O]^+$ and [Tb$(ODA){\cdot}(phen){\cdot}4H_2O]^+$ in the crystalline state (Q = 17.7 and Q = 56.6%, respectively) are much greater than those of [Eu($ODA)_3]^{3-}and\;[Tb(ODA)_3]^{3-}$(Q = 1.1 and Q = 1.3, respectively), due to the energy transfer from phen to the lanthanide ion. In the aqueous state, the relaxation of the phen moiety due to the solvent results in the reduction of the quantum yield and the shortening of the lifetime.

Synthesis and Crystal Structures of Mn(II)- and Ni(II)-Dicarboxylate Complexes with 1,10-Phenanthroline

  • Koo, Bon-Kweon
    • Bulletin of the Korean Chemical Society
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    • v.33 no.7
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    • pp.2299-2304
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    • 2012
  • Two new metal(II) complexes, $[Mn(dpa)(phen)(H_2O)_2]_n$ (1) ($H_2dpa$ = dephenic acid, phen = 1,10-phenanthroline) and $[Ni_2(nda)(phen)_2(H_2O)_6](nda)(H_2O)$ (2) ($H_2nda$ = 2,6-naphthalenedicarboxylic acid) have been synthesized and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and single crystal X-ray diffraction. In complex 1, Mn(II) ion is six-coordinated, and Mn(II) ions are bridged by dpa ligands into 1D chains. While, the complex 2 is dimer and two Ni(II) ions are bridged by one nda ligand cooperated with the terminal ligand phen. In each complex, the dicarboxylate ligand is coordinated to metal(II) ions as a bis-monodentate.

Binding Modes of New Bis-Ru(II) Complexes to DNA: Effect of the Length of the Linker

  • Kwon, Byung-Hyang;Choi, Byung-Hoon;Lee, Hyun-Mee;Jang, Yoon-Jung;Lee, Jae-Cheol;Kim, Seog-K.
    • Bulletin of the Korean Chemical Society
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    • v.31 no.6
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    • pp.1615-1620
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    • 2010
  • Bis-[dipyrido[3,2-$\alpha$:2',3'-c]phenazine)$_2$(1,10-phenanthroline)$_2Ru_2$]$^{2+}$ complexes (bis-Ru(II) complexes) tethered by linkers of various lengths were synthesized and their binding properties to DNA investigated by normal absorption and linear dichroism spectra, and fluorescence techniques in this study. Upon binding to DNA, the bis-Ru(II) complex with the longest linker (1,3-bis-(4-pyridyl)-propane), exhibited a negative $LD^r$ signal whose intensity was as large as that in the DNA absorption region, followed by a complicate $LD^r$ signal in the metal-to-ligand charge transfer region. The luminescence intensity of this bis-Ru(II) complex was enhanced. The observed $LD^r$ and luminescence results resembled that of the [Ru(1,10-phenanthroline)$_2$ dipyrido[3,2-$\alpha$:2',3'-c]phenazine]$^{2+}$ complex, whose dipyrido[3,2-$\alpha$:2',3'-c]phenazine (dppz) ligand has been known to intercalate between DNA bases. Hence, it is conclusive that both dppz ligands of the bis-Ru(II) complex intercalate. The binding stoichiometry, however, was a single intercalated dppz per ~ 2.3 bases, which violates the "nearest binding site exclusion" model for intercalation. The length between the two Ru(II) complexes may be barely long enough to accommodate one DNA base between the two dppz ligands, but not for two DNA bases. When the linker was shorter (4,4'-bipyridine or 1,2-bis-(4-pyridyl)-ethane), the magnitude of the LD in the dppz absorption region, as well as the luminescence intensity of both bis-Ru(II) complexes, was half that of the bis-Ru(II) complex bearing a long linker. This observation can be elucidated by a model whereby one of the dppz ligands intercalates while the other is exposed to the aqueous environment.

Chemical Equilibria of Lanthanide {Ln(III)=Pr, Sm, Gd, Dy}-Macrocyclic Complexes with Auxiliary Ligands in $CH_3OH$(Part III); Study of the Coordination of Nitrogen-or Oxygen-Containing Bases ($CH_3OH$ 용매에서 란탄족 원소 {Ln(III)=Pr, Sm, Gd, Dy}-거대고리 착물과 보조리간드 간의 화학평형(제3보); 두자리 리간드(주게원자:N혹은 O)를 중심으로 고찰)

  • Byun, Jong-Chul;Park, Yu-Chul;Han, Chung-Hun
    • Journal of the Korean Chemical Society
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    • v.44 no.2
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    • pp.95-101
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    • 2000
  • Macroacyclic transition metal complexes such as $Cu(H_2L[A]).H_2O$, $Cu(H_2L[B]).H_2O$, CuFe(L[A]($NO_3$).$4H_2O$, CuFe(L[B])($NO_3$).$4H_2O$, [$CuGd(H_2L[A])(NO_3)_2](NO_3).2CH_3OH$, [CuGd($H_2L$[B])($NO_3)_2$]($NO_3).2CH_3OH were prepared from the corresponding hexadentate compartmental ligands, $H_4L[A]$ and $H_4L[B]$, which were obtained by the condensation of 2-hydroxy-3-hydroxymethy1-5-methyIbenzaldehyde(HHNNB) and ethylenediamine or l,3-diaminopropane. Ln-macrocyclic([20]DOTA) complexes,[Ln([20]DOTA)($NO_3)(H_2O)$]($NO_3$)2.$xH_2O${Ln(III)=Pr, Sm, Gd, Dy, which had been synthesized from 2,6-diformyl-p-cresol(DFPC), was placed in methanol for 2 days, and [Ln([20] DOTA)($NO_3)(CH_3OH)]^{2+}$ was formed The equilibrium constants (k) for the substitution of coordinated $CH_3OH$ in the Ln-[20]DOTA complexes by various bidentate auxiliary ligands, $L_a$(=o-phenylenediamine,1,10-phenanthroline, ethylenediamine,oxalicacid, malonic acid, acethylacetone) were determined by spectroscopic method at $25^{\circ}C$ and 0.1M $NaClO_4$.The pKa of auxiliary ligands is in the order of o-phenylenediamine < 1,10-phenanthroline < ethylene-diamine, oxalic acid < malonic acid < acethylacetone. However, the equilibrium constant(K) has shown thetrend of ethyleneiamine < 1,10-phenanthroline < o-phenylenediamine, acethylacetone < malonic acid < oxalic acid.

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Studies on Solvent Sublation of Trace Heavy Metals by Continuous Flow System as Ternary Complexes of 1,10-Phenanthroline and Thiocyanate Ion

  • Kim, Young-Sang;Choi, Yoon-Seok;Lee, Won
    • Bulletin of the Korean Chemical Society
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    • v.24 no.12
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    • pp.1775-1780
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    • 2003
  • A continuous flow system has been developed to determine trace Cu(II), Mn(II), Ni(II) and Zn(II) in a large volume of water samples by a solvent sublation technique. The mixed solution of 1,10-phenanthroline(phen) and thiocyanate ion was used as ligands for the formation of their ternary complexes. The continuous system was constructed in this laboratory with a peristaltic pump, a mini shaker, three mixing bottles and a flotation cell by connecting each part with a polyethylene tube. The flotation conditions such as the flow rate of sample solution and the injection rates of ligand, buffer and surfactant solutions have been investigated to obtain the best sublation efficiencies. Each solution flowed into the flotation cell through each polyethylene tube by the peristaltic pumps. The ternary complexes were floated and extracted into MIBK in a flotation cell of 2 L by bubbling a nitrogen gas. The absorbances of extracted analytes in MIBK were directly measured by graphite furnace-AAS. The concentrations of 1,10-phenanthroline and thiocyanate ion were $2.6\;{\times}\;10^{-3}$ M and $2.3\;{\times}\;10^{-2}$ M in the mixed solution, respectively. The pH of sample solution was adjusted to 5.0 with a buffer solution and 1%(m/v) sodium lauryl sulphate solution was added as a surfactant to support the effective flotation of the complexes. The $N_2$ gas was bubbled at 30 mL/min for 90 minutes for 20 L of sample. Reproducible results of less than 10% RSD and recoveries of 80-120% could be obtained in real samples.