• Bulletin of the Korean Chemical Society
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• v.33 no.11
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• pp.3581-3588
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• 2012

A new series of acyclic mononuclear gadolinium(III) complexes have been prepared by Schiff-base condensation derived from 5-methylsalicylaldehyde, diethylenetriamine, tris(2-aminoethyl) amine, triethylenetetramine, N,N-bis(3-aminopropyl)ethylene diamine, N,N-bis(aminopropyl) piperazine, and gadolinium nitrate. All the complexes were characterized by elemental and spectral analyses. Electronic spectra of the complexes show azomethine (CH=N) within the range of 410-420 nm. The fluorescence efficiency of Gd(III) ion in the cavity was completely quenched by the higher chain length ligands. Electrochemical studies of the complexes show irreversible one electron reduction process around -2.15 to -1.60 V The reduction potential of gadolinium(III) complexes shifts towards anodic directions respectively upon increasing the chain length. The catalytic activity of the gadolinium(III) complexes on the hydrolysis of 4-nitrophenylphosphate was determined. All gadolinium(III) complexes were screened for antibacterial activity.

• The Journal of Natural Sciences
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• v.5 no.1
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• pp.77-86
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• 1992

By cation-exchange-reaction long-chain organic cationic tensides can be intercalated in the montmorillonite layer space, and thus intercalations-complexes of montmorillonite with different properties of materials can be obtained. Such intercalations-complexes are finding strong technical appliances in many areas and are also used very often as model-systems for studying behaviors of materials. Therefore in this research intercalations-complexes of montmorillonite with organic cationic tensides ad model-systems were synthesized and their behabiors under various different conditions were studied.

• Korean Journal of Food Science and Technology
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• v.46 no.2
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• pp.180-188
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• 2014

This study focused on assessing the solubility and structural characteristics of two types of coenzyme $Q_{10}$ ($CoQ_{10}$) complexes: the $CoQ_{10}$-starch and the $CoQ_{10}$-cyclodextrin complexes. The solubility of $CoQ_{10}$-starch complex increased significantly as the temperature was increased. However, the solubility of $CoQ_{10}$-cyclodextrin complex reached a peak at $37^{\circ}C$, and strong aggregation occurred at $50^{\circ}C$. When the temperature was raised to $80^{\circ}C$, the $CoQ_{10}$-cyclodextrin complex dissociated owing to the weakening of bonds, resulting in $CoQ_{10}$ emerging at the surface of water. Therefore, $CoQ_{10}$-cyclodextrin complexes have lower solubility, due to their reduced heat-stability, than do the $CoQ_{10}$-starch complexes. Structural differences between the two $CoQ_{10}$ complexes were confirmed by Fourier transform infrared (FT-IR) spectroscopy, X-ray diffractometer (XRD), and differential scanning calorimeter (DSC). The $CoQ_{10}$-cyclodextrin complex included an isoprenoid chain of $CoQ_{10}$, while the $CoQ_{10}$-starch complex included both the benzoquinone ring and the isoprenoid chain of $CoQ_{10}$. These results suggest that $CoQ_{10}$-starch complexes possess higher heat-stability and solubility than do the $CoQ_{10}$-cyclodextrin complexes.

• Bulletin of the Korean Chemical Society
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• v.33 no.9
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• pp.2917-2924
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• 2012

Four novel metal-organic complexes $[Cd_2(IP)_2(TBZ)_2(H_2O)_2]{\cdot}(H_2O)$ (1), $[Zn_4(IP)_4(TBZ)_4]{\cdot}2(H_2O)$ (2), $[Zn_2(BTC)(TBZ)_2(CO_2H)]$ (3), [Co(PDC)(TBZ)] (4) (where IP = isophthalate; TBZ = thiabendazole; BTC = 1,3,5-benzenetricarboxylate; PDC = pyridine-3,4-dicarboxylate) have been prepared and characterized by IR spectrum, elemental analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. X-ray structure analysis reveals that 1, 2, and 3 are one-dimensional chain polymers, while 4 is a two-dimensional network polymer. The TBZ acts as a typical chelating ligand coordinated to the metal center in all complexes. The 1D chain architecture of 1 is constructed from isophthalates and cadmium atoms. A simultaneous presence of chelating, monodentate and bidentate coordination modes of IP ligands is observed in complex 2. In complex 3, the 16-membered rings are alternately arranged forming an infinite 1D double-chain structure. The 2D skeleton of 4 is formed by cobalt ions as nodes and PDC dianions as spacers, through coordination bonds. The hydrogen bonds and ${\pi}-{\pi}$ stacking play important roles in affecting the final structure where complexes 1 and 3 have 2D supramolecular networks, while complexes 2 and 4 have 3D supramolecular architectures.

• Bulletin of the Korean Chemical Society
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• v.25 no.10
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• pp.1477-1483
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• 2004

We present the tandem mass spectrometry applications carried out to elucidate the coordination structure of Zn(II) bound lysine ternary complexes, $(Zn+Lys+Lys-H)^+$, which is a good model system to represent a simple (metallo)enzyme-substrate complex (ES). In particular, experimental efforts were focused on revealing the involvement of a lysine side chain ${\varepsilon}$-amino group in the coordination of $Zn^{2+}$ divalent ions. MS/MS fragmentation pattern showed that all the oxygen species within a complex fell off in the form of $H_2O$ in contrast to those of other ternary complexes containing amino acids with simple side chains (4-coordinate geometries, Figure 1a), suggesting that the lysine complexes have different coordination structures from the others. The participation of a lysine basic side chain in the coordination of Zn(II) was experimentally evidenced in MS/MS for $N{\varepsilon}$-Acetyl-L-Lys Zn(II) complexes with acetyl protection groups as well as in MS/MS for the ternary complexes with one $NH_3$ loss, $(Zn+Lys+Lys-NH_3-H)^+$. Detailed structures were predicted using ab initio calculations on $(Zn+Lys+Lys-H)^+$ isomers with 4-, 5-, and 6-coordinate structures. A zwitterionic 4-coordinate complex (Figure 7d) and a 5-coordinate structure with distorted bipyramidal geometry (Figure 7b) are found to be most plausible in terms of energy stability and compatibility with the experimental observations, respectively.

• Journal of the Korean Chemical Society
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• v.36 no.5
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• pp.770-779
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• 1992

Five (alkynylethoxymethylene)$Fe(CO)_4 complexes (1) are prepared through the reaction of Fe(CO)_5$ with alkynyllithium (R = n-Pr, cyclohexyl, t-Bu, trimethylsilyl, Ph) and subsequent O-ethylation of the resulting acyl anion complexes with ethyl fluorosulfonate. In the reactions of trimethylsilyl-substituted alkynylcarbene complex (1d) with 8 open-chain 1,3-dienes, ({\eta}^3-vinylcarbene)Fe(CO)3 complexes (2) are obtained as major products.

• Journal of Electrochemical Science and Technology
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• v.14 no.2
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• pp.152-161
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• 2023

Vanadium redox flow batteries (VRFBs) have been considered one of promising power sources for large scale energy storage systems (ESS) because of their excellent cycle performance and good safety. However, VRFBs still have a few challenging issues, such as poor Coulombic efficiency due to vanadium crossover between catholyte and anolyte, although recent efforts have shown promise in electrochemical performance. Herein, the vanadium complexes with various glyme ligands have been examined as active materials to suppress vanadium crossover between catholyte and anolyte, thus improving the Coulombic efficiency of VRFBs. The conventional Nafion membrane has a channel size of ca. 10 Å, whereas vanadium cation species are small compared to the Nafion membrane channel. For this reason, vanadium cations can permeate through the Nafion membrane, resulting in significant vanadium crossover during cycling, although the Nafion membrane is a kind of ion-selective membrane. In this regard, various glyme additives, such as 1,2-dimethoxyethane (monoglyme), diethylene glycol dimethyl ether (diglyme), and tetraethylene glycol dimethyl ether (tetraglyme) have been examined as complexing agents for vanadium cations to increase the size of vanadium-ligand complexes in electrolytes. Since the size of vanadium-glyme complexes is proportional to the chain length of glymes, the vanadium permeability of the Nafion membrane decreases with increasing the chain length of glymes. As a result, the vanadium complexes with tetraglyme shows the excellent electrochemical performance of VRFBs, such as stable capacity retention (90.4% after 100 cycles) and high Coulombic efficiency (98.2% over 100 cycles).

• Bulletin of the Korean Chemical Society
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• v.12 no.2
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• pp.219-224
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• 1991

New binuclear Ni(Ⅱ) and Cu(Ⅱ) complexes with various alkyl derivatives of 1,2-bis(1,3,6,8,10,13-hexaaza-1-cyclotetradecyl) ethane, in which two fully saturated 14-membered hexaaza macrocyclic subunits are linked together by an ethylene chain, have been synthesized by the one step template condensations of formaldehyde with ethylenediamine and appropriate primary alkyl amines in the presence of the metal ions. Each macrocyclic subunit of the double-ring macrocyclic complexes contains one alkyl pendant arm and has a square planar geometry with a 5-6-5-6 chelate ring sequence. The visible spectra and oxidation properties indicate that the metal-metal interaction of the binuclear complexes are not significant. Synthesis, characterization, and the properties of the complexes are presented.

• Bulletin of the Korean Chemical Society
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• v.33 no.5
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• pp.1581-1585
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• 2012

Two pyridinecarboxamide dicyanidecobalt(III) building blocks and two mononuclear seven-coordinated macrocycle manganese(II) compounds have been rationally selected to assemble cyanide-bridged heterobimetallic complexes, resulting in three cyanide-bridged $Co^{III}-Mn^{II}$ complexes. Single X-ray diffraction analysis show that these complexes $\{[Mn(L^1)][Co(bpb)]\}ClO_4{\cdot}CH_3OH{\cdot}0.5H_2O$ ($\mathbf{1}$), $\{[Mn(L^2)][Co(bpb)]\}ClO_4{\cdot}0.5CH_3OH$ ($\mathbf{2}$) and ${[Mn(L^1)][Co(bpb)]\}ClO_4{\cdot}H_2O$ ($\mathbf{3}$) ($L^1$ = 3,6-diazaoctane-1,8-diamine, $L^2$ = 3,6-dioxaoctano-1,8-diamine; $bpb2^{2-}$ = 1,2-bis(pyridine-2-carboxamido)benzenate, $bpmb2^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate) all present predictable one-dimensional single chain structures. The molecular structures of these one-dimensional complexes consists of alternating units of $[Mn(L)]^{2+}$ ($L=L^1$ or $L^2$) and $[Co(L^{\prime})(CN)2]^-$ ($L^{\prime}=bpb2^{2-}$, or $bpmb2^{2-}$), forming a cyanide-bridged cationic polymeric chain with free $ClO_4{^-}$ as the balance anion. The coordination geometry of manganese(II) ion in the three one-dimensional complexes is a slightly distorted pentagonal-bipyrimidal with two cyanide nitrogen atoms at the trans positions and $N_5$ or $N_3O_2$ coordinating mode at the equatorial plane from ligand $L^1$ or $L^2$. Investigation over magnetic properties of these complexes reveals that the very weak magnetic coupling between neighboring Mn(II) ions connected by the diamagnetic dicyanidecobalt(III) building block. A best-fit to the magnetic susceptibility of complex ${\mathbf}{1}$ leads to the magnetic coupling constants $J=-0.084(3)cm^{-1}$.

• Bulletin of the Korean Chemical Society
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• v.28 no.8
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• pp.1299-1304
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• 2007

New sulfur functionalized cyclopentadiene ligands, 1-[2-(thioanisole)]-2,5-dimethylcyclopentadiene (3), 1-[2- (thioanisole)]-2,3,5-trimethylcyclopentadiene (4), and 1-[2-(thioanisole)]-2,3,4,5-tetramethylcyclopentadiene (5), were prepared. In these ligands, the S-donor atom is connected to a cyclopentadiene ring by a rigid phenylene spacer. CpCo(III)-diiodo half-sandwich complexes (6-8) were obtained from reaction the ligands (3- 5) with Co2(CO)8, followed by treatment of I2. Substitution reaction of CpCo(III)-diiodo complexes with MeLi yielded the corresponding CpCo(III)-dimethyl complexes (9-11). Further transformation to the corresponding cationic cobalt complexes (12-14) were achieved by reaction of the CpCo(III)-dimethyl complexes with HB(ArF)4·2Et2O and trapping with CD3CN. The new sulfur functionalized cyclopentadiene ligands having a rigid phenylene spacer and the corresponding cobalt complexes were characterized by 1H, 13C and 19F NMR spectroscopy. The diiodo Complex 6 was also characterized by a single crystal X-ray diffraction method.