• Journal of the Korean Chemical Society
• /
• v.35 no.4
• /
• pp.368-373
• /
• 1991

Palladium(II) complexes of the type Pd(IEAA-NR)$_2$ (R = H, CH$_3$, C$_2$H$_5$, n-C$_3$H$_7$, n-C$_4$H$_9$, or CH$_2$C$_6$H$_5$), where IEAA-NR represents N-alkyl derivative of isonitrosoethylacetoacetate (H-IEAA) imine, have been prepared. And the structure of the complexes have been studied by elemental analyses, electronic, infrared, $^1$H and $^{13}$C-NMR spectra. It is proposed that both of IEAA-NR ligands coordinate to metal through nitrogens of imine and isonitroso groups to form 5-membered chelate rings in the complexes.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
• /
• 1999.11a
• /
• pp.529-532
• /
• 1999

본 연구에서는 유기 전기 발광 소자에서 녹색 발광층으로 사용되는 terbium(Tb) complexes와 europium(Eu) complex, 정공 수송층으로 사용되는 TPD (N, N\`-diphenyl-N,\`(3-methylphenyl)-1, 1\`biphenyl-4, 4\`-diamine), 그리고 전자 수송층으로 사용되는 Alq$_{3}$ (trois(8-hydroxyquinolino)aluminum), Bebq$_2$들의 Uv/Vis. 홉광도와 PL 스펙 트럼과 같은 광학적 특성을 조사하였으며 또한 이러한 물질들을 이용하여 다양한 종류의 유기 전기 발광 소자를 제작하고 제작된 소자들의 전류밀도-전압-조도 등의 전기 . 광학적 특성을 조사하였으며, 그 결과 다 음과 같은 결곤을 얻을 수 있었다. 다양한 ligand를 갖는 Tb complex들의 경우에도 EL 스펙트럼의 파장대 (wavelength)는 546nm~548nm의 녹색 발광을 하는 것을 알 수 있었고, 제작된 소자 중에서 Tb(ACAC)$_3$(Phen) 을 발광충으로 하고, TPD, 그리고 Bebq$_2$를 각각 정공 수송층, 전자 수송 층으로 한 소자가 가장 낮은 구동 전압을 갖는다는 것을 확인하였으며 logJ-logV 특성에서도 모든 전계 구간에서 이러한 구조의 소자가 가장 높은 전류밀도를 나타냈으며 저 전계 구간에서 전류밀도 타이가 가장 컸다. 소자의 전류밀도와 휘도의 관계에 있어서는 제작된 네 종류의 소자 중 Tb(ACAC)3(Cl-Phen)를 발광층으로 하고 TPD, 그리고 Bebq2를 각각 정공 수송층, 전자 수송 층으로 한 소자가 가장 휘도가 우수한 것을 알 수 있었다. 또한 red (europium complex), green (terbium complex), 그리고 blue (TPD) 색깔을 나타내는 유기 재료를 사용하여 한 소자에서 백색 소자를 제작하여 cyclic voltametric방법을 이용하여 각 유기 물질들의 에너지 준위를 조사하여, 각각의 소자들을 에너지 밴드 다이어그램(energy band diagram)으로 자세히 설명하였다.

• Bulletin of the Korean Chemical Society
• /
• v.19 no.6
• /
• pp.671-676
• /
• 1998

The formation and dissociation rates of $Ce^{3+}$ Complexes of the 1,4,7,10-tetraaza-13,16-dioxacyclooctadecane-NN', N",N"'-tetraacetic acid (1), 1,4,7,10-tetraaza-13,16-dioxacyclooctadecane-N,N',N",N"'-tetramethylacetic acid (2), and 1,4,7,10-tetraaza-13,16-dioxacyclooctadecane-N,N',N",N"'-tetrapropionic acid (3) have been measured by the use of stopped-flow spectrophotometry. Observations were made at 25.0±0.1 ℃ and at an ionic strength of 0.10 M $NaClO_4$. The complexation of $Ce^{3+}$ ion with 1 and 2 proceeds through the formation of an intermediate complex $(CeH_3L^{2+})^*$ in which the $Ce^{3+}$ ion is incompletely coordinated. This may then lead to be a final product in the rate-determining step. Between pH 4.76 and 5.76, the diprotonated $(H_2L^{2-})$ from is revealed to be a kinetically active species despite of its low concentration. The stability constants $(logK(CeH_3L^{2+}))$ and specific water-assisted rate constants $(k_{OH})$ of intermediate complexes have been determined from the kinetic data. The dissociation reactions of $Ce^{3+}$ complexes of 1, 2, and 3 were investigated with $Cu^{2+}$, ions as a scavenger in acetate buffer. All complexes exhibit acid-independent and acid-catalyzed contributions. The effect of buffer and $Cu^{2+}$ concentration on the dissociation rate has also been investigated. The ligand effect on the dissociation rate of $Ce^{3+}$ complexes is discussed in terms of the side-pendant arms and the chelate ring sizes of the ligands.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
• /
• v.9 no.4
• /
• pp.207-217
• /
• 2011

In this study the complex formation reactions between uranium(VI) and 2,6-dihydroxybenzoate (DHB) as a model ligand of humic acid were investigated by using UV-Vis spectrophotometry and time-resolved laser-induced fluorescence spectroscopy (TRLFS). The analysis of the spectrophotometric data, i.e., absorbance changes at the characteristic charge-transfer bands of the U(VI)-DHB complex, indicates that both 1:1 and 1:2 (U(VI):DHB) complexes occur as a result of dual equilibria and their distribution varies in a pH-dependent manner. The stepwise stability constants determined (log $K_1$ and log $K_2$) are $12.4{\pm}0.1$ and $11.4{\pm}0.1$. Further, the TRLFS study shows that DHB plays a role as a fluorescence quencher of U(VI) species. The presence of both a dynamic and static quenching process was identified for all U(VI) species examined, i.e., ${UO_2}^{2+}$, $(UO_2)_2{(OH)_2}^{2+}$, and $(UO_2)_3{(OH)_5}^+$. The fluorescence intensity and lifetimes of each species were measured from the time-resolved spectra at various ligand concentrations, and then analyzed based on Stern-Volmer equations. The static quenching constants (log $K_s$) obtained are $4.2{\pm}0.1$, $4.3{\pm}0.1$, and $4.34{\pm}0.08$ for ${UO_2}^{2+}$, $(UO_2)_2{(OH)_2}^{2+}$, and $(UO_2)_3{(OH)_5}^+$, respectively. The results of Stern-Volmer analysis suggest that both mono- and bi-dentate U(VI)-DHB complexes serve as groundstate complexes inducing static quenching.

• Journal of the Korean Chemical Society
• /
• v.39 no.3
• /
• pp.198-203
• /
• 1995

The Mo(V) $di-\mu-oxo$ type $(Mo_2O_4(H_2O)_2L)$ complexes $(L:\;C_3H_7CH(SCH_2COOH)_2,\;C_6H_5CH(SCH_2COOH)_2,\;CH_3OC_6H_4CH(SCH_2COOH)_2,\;C_5H_{10}C(SCH_2COOH)_2,\;C_3H_7C(CH_3)(SCH_2COOH)_2,\;C_3H_7CH(SCH_2CH_2COOH)_2,\;C_6H_5CH(SCH_2CH_2COOH)_2)$ have been prepared by the reaction of $[Mo_2O_4(H_2O)_6]^{2+}$ with a series of dithiodicarboxy ligands. These complexes are completed by two terminal oxygens arranged trans to one another and each ligand forms a chelate type between two molybdenum. In $Mo_2O_4(H_2O)_2L$, two $H_2O$ coordinated at trans site of terminal oxygens. The prepared complexes have been characterized by elemental analysis, infrared spectra, electronic spectra, and nuclear magnetic resonance spectra. In the potential range -0.00 V to -1.00 V at a scan rate of 20 $mVs^{-1}$, a cathodic peak at -0.50∼-0.58 V (vs. SCE) and an anodic peak at -0.40∼-0.43 V (vs. SCE) have been observed in aquous solution. The ratio of the cathodic to anodic current ($I_{pc}/I_{pa}$) is almost 1, we infer that redox is reversible reaction.

• Journal of the Korean Chemical Society
• /
• v.37 no.7
• /
• pp.655-661
• /
• 1993

The neutral monomeric compounds $[Mo(NO)_2Cl_2(phen)]$ and $[W(NO)_2Cl_2(phen)]$ (phen= 1,10-phenanthroline) have been prepared by reactions of polymeric compounds $[{Mo(NO)_2Cl_2}n],\;[{W(NO)_2Cl_2}n]$ with chelate ligands. Additions of one equivalent of silver(I) perchlorate to these cis-dinitrosyl compounds in acetone solution produce $[Mo(NO)_2(phen)(S)Cl][ClO_4]\;and\;[W(NO)_2(phen)(S)Cl][ClO_4]$ (S = acetone). The homo- and hetero-dinuclear complexes, $[Cl(phen)(NO)_2M(pyz)M'(NO)_2(phen)Cl][ClO_4]_2$ (M = Mo, W) and $[Cl(phen)(NO)_2M(pyz)M'(NO)_2(phen)Cl][C1O_4]_2$ (M = Mo, M' = W) have been prepared by these monocationic complexes with pyrazine ligand respectively. These complexes characterized by elemental analysis, $1^H-\;and\;^{13}C-NMR$, infrared, and UV-visible spectroscopy are reported. The spectral data indicate that homo- and hetero-dinuclear complexes were symmetrical structures of $C_{2v}$.

• Progress in Medical Physics
• /
• v.17 no.2
• /
• pp.61-66
• /
• 2006

To evaluate the T1, T2 magnetic relaxation properties of water molecule according to molecular weight of paramagnetic complex. 4-aminomethyicyclohexane carboxylic acid (0.63 g, 4 mmol) was mixed with the suspension solution of DMF (15 ml) and DTPA-bis-anhydride (0.71 g, 2 mmol) to synthesize the ligand. The ligand was then mixed with $Gd_2O_3$ (0.18 g, 0.5 mmol) to synthesize Gd-chelate. For the measurement of magnetic relaxivity of paramagnetic compounds, the compounds were diluted to 1 mM and then the relaxation times were measured at 1.57 (64 MHz). Inversion-recovery pulse sequence was employed for T1 relaxation measurement and CPMG (Carr-Purcell-Meiboon-Gill) pulse sequence was employed for T2 relaxation measurement. In case of inversion recovery sequence, total 35 images with different inversion time(T1)s ranging from 50 msec to 1,750 msec. To estimate the relaxation times, the signal intensity of each sample was measured using region of Interest (ROI) and then fitted by non-linear least square method to yield T1, T2 relaxation times and also R1 and R2. Compared to T1=($205.1{\pm}2.57$) msec and T2=($209.4{\pm}4.28$) msec of Omniscan (Gadodiamide), which is commercially available paramagnetic MR agent, T1 and T2 values of new paramagnetic complexes were reduced along with their molecular weight. That is, T1 value was ranged from $(96.35{\pm}2.04)\;to\;(79.38{\pm}1.55)$ msec and T2 value was ranged from $(91.02{\pm}2.08)\;to\;(76.66{\pm}1.84)$ msec. Among new paramagnetic complexes, there is a tendency that the R1 and R2 increase as the molecular weight is increases. As molecular weight of paramagnetic complex increases, T1 and T2 relaxation times reduce and thus the increase of relaxivity (R1 and R2) Is proportional to molecular weight.

• Investigative Magnetic Resonance Imaging
• /
• v.10 no.1
• /
• pp.20-25
• /
• 2006

Purpose : To evaluate the NMR relaxation properties of newly developed high performance paramagnetic complexes. Materials and methods : 4-aminomethylcyclohexane carboxylic acid (0.63g, 4 mmol) was mixed with the suspension solution of DMF (15mL) and DTPA-bis-anhydride (0.71g, 2 mmol) to synthesize the ligand. The ligand was then mixed with Gd2O3 (0.18g, 0.5 mmol) to synthesize Gd-chelate. For the measurement of magnetic relaxivity of paramagnetic compounds, the compounds were diluted to 1mM and then the relaxation times were measured at 1.5T(64 MHz). Inversion-recovery pulse sequence was employed for T1 relaxation measurement and CPMG(Carr-Purcell-Meiboon-Gill) pulse sequence was employed for T2 relaxation measurement. Using MATLAB(Version 7.1) program, T1 magnetic relaxation map, R1 map, T2 magnetic relaxation map and R2 map were developed to represent magnetic relaxation time and magnetic relaxivity as image. Results : Compared to $R1=4.9mM^{-1}sec^{-1}$ and $R2=4.8mM^{-1}sec^{-1}$ of Omniscan (Gadodiamide), which is commercially available paramagnetic MR agent, R1 of SUK090(Gd-C32H74N5O24) was $12.46mM^{-1}sec^{-1}$ and R1 of SUK091(Gd-C34H78N5O24) was $12.77mM^{-1}sec^{-1}$. However, R1 of SUK092(Gd-C30H56N5O17) was decreased to $2.09mM^{-1}sec^{-1}$. In case of R2, SUK090(Gd-C32H74N5O24) was $8.76mM^{-1}sec^{-1}$ and SUK091(Gd-C34H78N5O24) was $7.60mM^{-}1sec^{-1}$ whereas SUK092(Gd-C30H56N5O17) was decreased to $1.82mM^{-1}sec^{-1}$. Conclusion : Among three new paramagnetic complexes, SUK090(Gd-C32H74N5O24) and SUK091(Gd-C34H78N5O24) showed higher T1, T2 magnetic relaxation rates than that of commercially available paramagnetic MR agent and thus expected to have more contrast enhancement effect.

• Journal of the Korean Chemical Society
• /
• v.44 no.5
• /
• pp.403-409
• /
• 2000

The formation and dissociation rates of $Zn^{2+}$ Complexes with l,4,7,10-tetraaza-13,16-diox-acyclooctadecane-N,N',N",N'"-tetraacetic acid (1), 1,4,7,10-tetraaza-13,16- dioxacyclooctadecane-N,N',N",N'"-tetramethylacetic acid (2), and 1,4,7,10-tetraaza-13,16- dioxacyclooctadecane-N,N',N",N'"-tetrapropionic acid(3) have been measured by stopped-flow and conventional spectrophotometry. Observations were made at 25.0$\pm$0.1 $^{\circ}C$ and at an ionic strength of 0.10 M NaClO$_4$. The formation reactions of $Zn^{2+}$ ion with 1 and 2 took place by the rapid formation of an intermediate complex (ZnH$_3L^+$) in which the $Zn^{2+}$ ion is incompletely coor-dinated. This might then lead to be a final product in the rate-determining step.ln the pH range 4.76-5.76, the diprotonated (H2L2-) form is the kinetically active species despite of its low concentration. The stability con-stants (log$K_{(ZnH$_3$3$L^+$)}$) and specific water-assisted rate constants (koH) of intermediate complexes have been deter-mined from the kinetic data. The dissociation reactions of $Zn^{2+}$ complexes of 1,2, and 3 were investigated with $Cu^{2+}$ ions as a scavenger in acetate buffer. All complexes exhibit acid-independent and acid-catalyzed con-tributions. The effect of buffer and $Cu^{2+}$ concentration on the dissociation rate has also been investigated. The ligand effect on t dissociation rate of $Zn^{2+}$ complexes is discussed in terms of the side-pendant armsand the chelate ring sizes of the ligands.