Haiil Ryu

Self-assembly of one-dimensional coordination polymer from nickel(II) macrocyclic complex and 2,6-pyridinedicarboxylate ligand

Abstract The reaction of [Ni(L)(H2O)2]Cl2 (L=2,5,9,12-tetramethyl-1,4,8,11-tetraazacyclotetradecane) with 2,6-pyridinedicarboxylate (pdc) generates one-dimensional coordination polymer [Ni(L)(pdc)]·H2O (1). In the polymeric framework, the nickel(II) ion has an octahedral geometry and is bridged by two pdc ligands. The magnetic susceptibility measurement for 1 exhibits a weak antiferromagnetic interaction ( J=−1.04(3) cm −1 ; H=−JΣSi·Si+1) between the S=1 nickel(II) paramagnetic centers.

Axial additions in nickel(II) complexes of 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane: syntheses and crystal structures of the octahedral nickel(II) complexes

Abstract The complex [NiL]Cl2 · 2H2O (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane) undergoes axial additions with monodentate ligands (X = N3−, NCS−1). The octahedral [NiLX2] complexes have been characterized and structures established by X-ray crystallography. The crystal structures of [NiL(N3)2] 1 and [NiL(NCS)2] 2 show that both structures are centrosymmetric and the nickel centre has an axially elongated octahedral geometry with two nitrogen atoms of the axial ligands. Electronic spectra and redox potentials of the complexes also reveal a high-spin octahedral geometry, which is reflected by the nature of the axial ligands.

Synthesis and characterization of nickel(II) complexes of a tetraaza macrocycle containing axial ligands

Abstract The octahedral complexes [NiLX2] (X=OH2 (1), ONO− (2) and NCO− (3); L=3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane) have been prepared and characterized by X-ray crystallography. The crystal structures of the [NiLX2] complexes have an axially elongated octahedral geometry with two axial ligands and adopt the trans-III configuration. Magnetic moments, electronic spectra and redox potentials of the [NiLX2] complexes also reveal a high-spin octahedral geometry, which is reflected by the nature of the axial ligands.

Synthesis, properties, and X-ray structure of [Cu(dpa)Cl2] (dpa = di-(2-picolyl)amine)

The mono(dpa)copper(II) complex [Cu(dpa)Cl2] (1) (dpa = di-(2-picolyl)amine) has been synthesized and structurally characterized. It crystallizes in the monoclinic system P21/n with a = 8.155(1), b = 12.560(1), c = 12.817(2) Å, β = 91.64(2)°, V = 1312.3(2) Å3, Z = 4. The copper atom is coordinated by three nitrogen atoms from the dpa ligand and two chlorides in a distorted square-pyramidal environment. Cyclic voltammetric data show that 1 undergoes the reversible one-electron oxidation to the Cu(III) and the reversible one-electron reduction to the Cu(I) state.

Synthesis and characterization of dicopper(II) and one-dimensional nickel(II) complexes with MO4 (M=Mo, W) as bridging ligands

The reaction of [M(L)]Cl 2 ·2H 2 O (M=Cu 2+ , Ni 2+ , and L=3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0 1.18 ,0 7.12 ]docosane) with [MO 4 ] 2− (M=Mo and W) in water–methanol solution yields dinuclear copper(II) and one-dimensional nickel(II) complexes, [{Cu II (L)} 2 (μ-MoO 4 )][MoO 4 ]·11H 2 O ( 1 ), [{Cu II (L)} 2 (μ-WO 4 )][WO 4 ]·11H 2 O ( 2 ), and catena -(μ-MoO 4 - O , O ′)[Ni II (L)]·5H 2 O ( 3 ). The crystal structures and the magnetic properties have been studied. Complexes 1 and 2 are isomorphous and the structures are made up of discrete dimers in which two copper(II) ions are bridged by the [MO 4 ] 2− anion. The cationic units of 3 are bridged by the [MoO 4 ] 2− anions to give a chain structure in the lattice. The coordination geometry about the copper(II) ions is a distorted square pyramid with the secondary amines of the macrocycle and an oxygen atom of [MO 4 ] 2− . However, each nickel(II) ion is coordinated by one macrocycle and two molybdate ligands in an octahedral trans arrangement elongated in the direction of the chain. Magnetic susceptibilities for 1 and 2 revealed that a ferromagnetic interaction between copper(II) ions is propagated through the [MO 4 ] 2− bridge and the coupling constants (2 J ) were calculated to be +2.5(1) cm −1 for [MoO 4 ] 2− and +5.9(1) cm −1 for [WO 4 ] 2− ( H =−2 J Σ S 1 S 2 ), respectively. In 3 , two nickel(II) ions bridged by the [MoO 4 ] 2− anion are antiferromagnetically coupled with the J value of −1.24(2) cm −1 ( H =− J Σ S i S i +1 ). Crystal data: 1 , monoclinic, space group P 2 1 , a= 9.651(1), b= 20.561(3), c= 14.794(5) A, β =99.03(2)°, V =2899.4(11) A 3 , Z= 2; 2 , monoclinic, space group P 2 1 , a= 9.683(1), b= 20.602(2), c= 14.882(6) A, β =99.00(2)°, V =2932.1(13) A 3 , Z= 2; 3 , triclinic, space group P 1, a= 10.089(1), b= 11.622(1), c= 13.433(2) A, α =113.46(1), β =100.01(1), γ =92.22(1)°, V =1412.8(3) A 3 , Z= 2.

Synthesis and properties of bridged phthalocyaninatoiron(II) complexes with bidentate aliphatic isocyanides

Phthalocyaninatoiron(II) (PcFe) was reacted with several aliphatic 5, 10–13, alicyclic 14, and aromatic isocyanides 3, 4 to form monomeric 15–17 and bridged oligomeric complexes 18–22. The syntheses of the isocyanides from the corresponding amines are described. All the products were characterized by spectroscopic methods. The coordination behaviour of the isocyanides based on their spectroscopic properties is discussed. The oligomers 18–22 show conductivities in the low semiconducting region, but by doping with iodine conductivities between 10−5 and 10−2 S/cm were obtained.

Magnesium isotope separation by ion exchange using hydrous manganese(IV) oxide.

The magnesium isotope effects were investigated by chemical ion exchange with a hydrous manganese(IV) oxide. The capacity of manganese(IV) oxide was 0.5 meq g(-1). The distribution coefficient of magnesium ions on the MnO(2) was determined by a batch method. The heavier isotopes of magnesium were enriched in the solution phase, while the lighter isotopes were enriched in the hydrous MnO(2) phase. The separation factor was determined according to the method of Glueckauf from the elution curve and isotopic assays. The separation factors of (24)Mg(2+)-(25)Mg(2+), (24)Mg(2+)-(26)Mg(2+), and (25)Mg(2+)-(26)Mg(2+) isotope pair fractionations were 1.011, 1.021, and 1.011, respectively.

Polymeric 2,3-naphthalocyaninatoiron(II) complexes with bidentate isocyanides as intrinsic semiconductors

Abstract 2,3-Naphthalocyaninatoiron(II) was reacted with monodentate and bidentate isocyanides to form monomeric and bridged polymeric complexes, respectively. The products were characterized by physical and spectrochemical methods. The bridged complexes show electrical conductivities in the range of 10−3–10−6 S/cm without additional doping.

A novel four-coordinate zinc(II) complex of the di-N-hydroxypropylated tetraaza macrocycle

The compound [Zn(L2)Cl]ClO4·H2O (1) (L2 = 2,13,-bis(3-hydroxypropyl)-5,16-di-methyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane) has been synthesized and structurally characterized. 1 crystallizes in the monoclinic system, space group P21/c with a = 8.932(2), b = 16.189(2), c = 22.492(4) Å β = 95.34(2)° V = 3238.3(11) Å3; and Z = 4. The zinc atom is placed in a highly distorted tetrahedral environment bonding with three nitrogen atoms of the macrocycle and one chlorine atom.

The Separation of Magnesium Isotopes by Tetraazamacrocycles Tethered to Merrifield Peptide Resin(TDM, TPM)

Tetraazamacrocyclic ion-exchangers, 1,4,8,11-tetraazacyclotetradecane bonded Merrifield peptide resin(TDM), 1,4,8,12-tetraazacyclopentadecane bonded Merrifield peptide resin(TPM) were prepared, and the ion-exchange capacity of these TDM and TPM were characterized. The distribution coefficients in various conc. of NH4Cl for magnesium with ion exchangers were determined by using the batch method. We found the isotope separation factors on new prepared tetraazamacrocyclic ion-exchangers bonded Merrifield peptide resin(TDM, TPM). The isotope separation of magnesium was determined by using of breakthrough method of column chromatography.