Jong-Ha Choi

Spectral properties and ligand field analysis of cis-dinitrito(1,4,8,11-tetraazacyclotetradecane)chromium(III) nitrate

Abstract The 77 K emission and excitation spectra, and 298 K infrared and absorption spectra of cis -[Cr(cyclam)(ONO) 2 ]NO 3 (cyclam=1,4,8,11-tetraazacyclotetradecane) have been measured. The vibrational intervals of the electronic ground state are extracted from the far-infrared and emission spectra. The 10 electronic bands due to spin-allowed and spin-forbidden transitions are assigned. Using the observed electronic transitions, a ligand field analysis was performed in the framework of the angular overlap model. It is confirmed that nitrogen atoms of the cyclam ligand have a strong σ-donor character, but nitrito ligand has weak σ- and π-donor properties toward chromium(III) ion.

Spectroscopic properties and ligand field analysis of cis-diazido(1,4,8,11-tetraazacyclotetradecane)chromium(III) azide.

The emission and excitation spectra of cis-[Cr(cyclam)(N3)2](N3) (cyclam = 1,4,8,11-tetraazacyclotetradecane) taken at 77 K are reported. The infrared and visible spectra at room temperature are also measured. The vibrational intervals due to the electronic ground state are extracted from the far-infrared and emission spectra. The ten electronic bands due to spin-allowed and spin-forbidden transitions are assigned. Using the observed transitions, a ligand field analysis has been performed to determine the bonding property of azido group in the chromium(III) complex. It is found that azide ligand has weak sigma- and pi-donor properties toward chromium(III) ion. The zero-phonon line in the excitation spectrum splits into two components by 249 cm(-1), and the large 2Eg splitting can be reproduced by the ligand field theory.

Optical ascorbic acid sensor based on the fluorescence quenching of silver nanoparticles.

A sensitive and selective fluorimetric sensor for the assay of ascorbic acid (AA) using silver nanoparticles as emission reagent was investigated. In this study, silver nanoparticles were prepared based on aqueous-gaseous phase reaction of silver nitrate solution and ammonia gas. The nanoparticles were water-soluble, stable and had a narrow emission band. They were used as a fluorescence probe for the assay of ascorbic acid on its quenching effect on the emission of silver nanoparticles. The principal reason for quenching is likely to be a complexation between ascorbic acid and silver nanoparticles. The quenching mechanism was established by Stern-Volmer law. Under the optimum conditions, the quenched fluorescence intensity was linear with the concentration of ascorbic acid in the range of 4.1 x 10(-6) to 1.0 x 10(-4) m (r = 0.9985) with a detection limit of 1.0 x 10(-7) m. The RSD for repeatability of the sensor for the assay of ascorbic acid concentration of 3.0 x 10(-5) and 4.0 x 10(-6) m was found to be 1.5 and 1.3%, respectively. The proposed method was applied to the determination of ascorbic acid in vegetables and vitamin C tablets.

Zinc(II) complexes of constrained antiviral macrocycles

The configurations of metallocyclams are of interest in relation to protein recognition and anti-HIV activity. We have synthesised four novel zinc(II) complexes with hexyl-Me(2)-cyclam (HMC; 3,14-dimethyl-2,6,13,17-tetraazatricyclo(16.4.0.0(7,12))docosane), 1, and naphthyl-hexyl-Me(2)-cyclam (NHMC; 2,13-bis(1-naphthylmethyl)-5,16-dimethyl-2,6,13,17-tetraazatricyclo(16.4.0.0(7,12))docosane), 2, as ligands. X-ray crystallographic data for Zn(II)-HMC diacetate, 3 show that zinc is six-coordinate in a distorted octahedral environment bound to four equatorial N atoms from the macrocycle and two axial acetato O atoms. The 14-membered metallo-macrocycle adopts a trans-III (RRSS) configuration with two six-membered rings in chair forms and two five-membered rings in gauche forms. In the chlorido Zn(II)-HMC complex 5, zinc appears to be 5-coordinate with square-pyramidal geometry. Interestingly, the chlorido Zn(II)-NHMC complex 6 crystallised in a trans-I configuration containing 4-coordinate tetrahedral zinc bound to three cyclam ring N atoms, a possible model for intermediates formed during the uptake and release of metals by cyclams. The ligand 1 and the zinc complex 3 were active towards viral strains HIV-1 (III(B)) (IC(50) values of 10.51 ± 0.23 and 3.50 ± 0.33 μM, respectively), and HIV-2 (ROD) (IC(50) values of 133.78 ± 14.10 and >110.67 μM, respectively). 2D [(1)H, (13)C] and [(1)H, (15)N] NMR spectroscopic studies suggested that the types of configurational isomers present in solution depend on the axial ligand.

Spectroscopic and ligand-field properties of [l-prolylglycinato][di(3-aminopropyl)amine]chromium(III) perchlorate

The mixed ligand complex [Cr(L-progly)(dpt)]ClO4 [H2progly = prolylglycine, dpt = di(3-aminopropyl)amine] has been prepared, and its geometric structure was discussed on the basis of electronic absorption and IR spectral data. The emission and excitation spectra taken at 77 K were also reported. The 12 electronic bands due to spin-allowed and spin-forbidden transitions were assigned. Using the electronic transitions, a ligand-field optimization has been performed to determine the metal-ligand bonding properties for the coordinated atoms. We confirmed that the peptide nitrogen of prolylglycinate has moderate strong sigma- and weak pi-donor properties toward chromium(III) ion.

Bis[trans‐dibromo(2,2‐di­methylpropane‐1,3‐diamine‐κ2N,N′)chromium(III)] dibromide hydrogen perchlorate hexahydrate

In the title compound, [CrBr(2)(C(5)H(14)N(2))(2)](2)Br(2).HClO(4).6H(2)O, there are two independent Cr(III) complex cations which are conformational isomers of each other. The Cr atoms lie respectively on a center of symmetry and on a mirror plane and have octahedral environments, coordinated by the N atoms of two 2,2-dimethylpropane-1,3-diamine ligands and by two Br atoms in trans positions. The Cr-N and Cr-Br bond lengths are in the ranges 2.078 (3)-2.089 (3) and 2.4495 (9)-2.5017 (9) A, respectively. The crystal structure consists of two Cr(III) complex cations, two Br(-) anions, a (ClO(4))(-) anion and an [H(13)O(6)](+) hydrogen-bonded cluster cation.

Synthesis, conformational structure and spectroscopic properties of trans-diazidobis(2,2-dimethyl-1,3-propanediamine)chromium(III) perchlorate.

A new complex trans-anti-[Cr(Me2tn)2(N3)2]ClO4·2H2O, where Me2tn=2,2-dimethyl-1,3-propanediamine was synthesized and characterized, and its molecular structure was established by single-crystal X-ray diffraction at 95K. The complex crystallized in the space group C2/c of the monoclinic system with four mononuclear formula units in a cell of dimensions a=16.600 (3), b=7.709 (2), c=16.865 (3)Å, and β=99.07 (3)°. The chromium(III) atom was in a distorted octahedral coordination with four N atoms of two chelating Me2tn ligands and two N atoms of the azido group in the trans axial position. The two six-membered rings in the complex adopted only anti chair-chair conformations with respect to each other The important bond lengths are CrN(azide) 2.007 (2), CrN(Me2tn) 2.081 (2), 2.082 (2), NN(azide) 1.184 (2) and 1.156 (2)Å, respectively. The crystal lattice is stabilized by hydrogen bonding interactions among the ClO4(-), hydrate molecule, N3(-), and NH groups of the Me2tn ligand. The ligand field analysis as well as the IR and electronic spectral properties were described.

Development of a sensitive flow‐injection–chemiluminescence detection method for the determination of laevodopa

A simple chemiluminometric method using flow injection has been developed for the determination of levodopa, based on its sensitizing effect on the weak chemiluminescence (CL) reaction between Na(2)SO(3) and acidic KMnO4. Under optimum experimental conditions, the CL intensity was linearly related to the concentration of levodopa from 3.4 x 10(-8) to 2.4 x 10(-5) mol/L and the detection limit was 1.1 x 10(-8) mol/L (s:n = 3). The relative standard deviation (RSD) of the proposed method calculated from 20 replicate injection of 3 x 10(-7) mol/L levodopa was 3.3%. The correlation coefficient was 0.997. The method was successfully applied to the determination of levodopa in commercial pharmaceutical formulations and spiked urine samples.

cis-(1,4,8,11-Tetra­aza­cyclo­tetra­decane-κN4)bis(­thio­cyanato-κN)chromium(III) thio­cyanate

The crystal structure of [Cr(NCS)2(cyclam)]NCS (cyclam = 1,4,8,11-tetraazacyclotetradecane, C10H24N4) has been determined by using synchrotron radiation at 98 K. The CrIII atom is in a slightly distorted octahedral environment with four N atoms of the macrocyclic ligand and two N-coordinated NCS− anions in cis positions. The average Cr—N(cyclam) and Cr—NCS bond lengths are 2.085 (5) and 1.996 (15) Å, respectively. In the crystal, the uncoordinating SCN− anion is hydrogen bonded through N—H⋯S and N—H⋯N interactions to neighbouring complex cations.

Crystal structure and conformational analysis of s-cis-(acetylacetonato)(ethylenediamine-N,N′-diacetato)-chromium(III)

AbstractThe crystal structure of [Cr(edda)(acac)] (edda = ethylediamine-N,N′-diacetate; acac = acetylacetonato) has been determined by a single crystal X-ray diffraction study at 150 K. The chromium ion is in a distorted octahedral environment coordinated by two N and two O atoms of chelating edda and two O atoms of acac, resulting in s-cis configuration. The complex crystallizes in the space group P21/c of the monoclinic system in a cell of dimensions a = 10.2588(9), b = 15.801(3), c = 8.7015(11) Å, β =101.201(9)° and Z = 4. The mean Cr-N(edda), Cr-O(edda) and Cr-O(acac) bond distances are 2.0829(14), 1.9678(11) and 1.9477(11) Å while the angles O-Cr-O of edda and O-Cr-O of acac are 171.47(5) and 92.72(5)°, respectively. The crystal structure is stabilized by N–H⋯O hydrogen bonds linking [Cr(edda)(acac)] molecules in distinct linear strands. The visible electronic and IR spectroscopic properties are also discussed. An improved, physically more realistic force field, Vibrationally Optimized Force Field (VOFF), capable of reproducing structural and vibrational properties of [Cr(edda)(acac)] was developed and its transferability demonstrated on selected chromium(III) complexes with similar ligands. Figure1D strand of hydrogen-bonded ···Δ -[Cr(R,R-edda)-(acac)]···Λ-[Cr(S,S-edda)(acac)]···in the crystal structure of [Cr(edda)(acac)]