• Bulletin of the Korean Chemical Society
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• 제18권9호
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• pp.976-981
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• 1997

The magnetic susceptibilities of molybdenum ions with 4d1 electronic configuration in the octahedral crystal field were calculated on the basis of ligand field theory. The experimental magnetic susceptibilities for molybdenum ions, which are stabilized at the octahedral site in the perovskite lattice of Ba2ScMoⅤO6 and Sr2YMoⅤO6, were compared with the theoretical ones. We have tried to fit their temperature dependence of magnetic susceptibility with ligand field parameters, spin-orbit coupling constant ζSO, and orbital reduction parameter κ according to intermediate field coupling and strong field theory. Strong field coupling theory could not explain experimental curves without unrealistically large axial ligand field, since it ignores the mixing up between different state via spin-orbit interaction and ligand field. On the other hand, the intermediate field coupling theory could successfully reproduce experimental data in octahedral and trigonal ligand field. The fitting result demonstrates not only the fact that spin-orbit interaction is primarily responsible for the variation of magnetic behavior but also the fact that effective orbital overlap, enhanced by cubic crystal structure, reduces significantly orbital angular momentum as indicated by κ parameter.

• Bulletin of the Korean Chemical Society
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• 제20권8호
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• pp.943-947
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• 1999

Ligand field analyses for tris(biuret)chromium(III) chloride and hexaureachromium(III) bromide were performed and compared to understand the ligand field properties of both ligands. The optimized eσO and eπO values indicate that coordinated oxygen atom in biuret ligand is a moderate s- and strong p-donor, while that in urea ligand is a weak σ- and moderate π-donor. The electronic structures of those two complexes are quite different and they were well accounted by inclusion of an anisotropic p bonding.

• Journal of Photoscience
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• 제11권1호
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• pp.19-23
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• 2004

The sharp-line absorption spectrum of microcrystalline samples of cis-[Cr(cycb)$Cl_2$]Cl (cycb=rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) has been measured between 13000 and $16000 cm^{-1}$ at temperatures down to 5K. The 77K emission and excitation spectra, and 298 K infrared and visible absorption spectra have also been measured. The nine electronic bands due to spin-allowed and spin-forbidden transitions were assigned. Using the observed transitions, a ligand field analysis has been performed to probe the ligand field properties of coordinated atoms in the title chromium(III) complex. The zero-phonon line in the sharp-line absorption spectrum splits into two components by $240 cm^{-1}$ , and the $large ^2$$_E{g}$ splitting can be reproduced by the modem ligand field theory. It is confirmed that nitrogen atoms of the macrocyclic cycb ligand have a strong $\sigma$-donor character, but chloride ligand has weak $\sigma$- nd $\pi$-donor properties toward chromium(III) ion.n.

• Bulletin of the Korean Chemical Society
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• 제19권5호
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• pp.575-579
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• 1998

The 77 K luminescence and excitation spectra, and 298 K infrared and absorption spectra of $cis-{\Alpha}-[Cr(trien)Cl_2]Cl{\cdot}H_2O$ (trien=triethylenetetramine) have been measured. Ligand field electronic transitions due to spin-allowed and spin-forbidden are assigned. The zero-phonon line in the excitation spectrum splits into two components by $198\; cm^{-1}$, and the large $^2E_g$ splitting can be reproduced by the modern ligand field theory. It is confirmed that nitrogen atoms of the trien ligand have a strong σ-donor character, but chloride ligand has weak σ- and π -donor properties toward chromium(III) ion.

• 대한화학회지
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• 제47권2호
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• pp.109-114
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• 2003

trans-$[CrX_2([15]aneN_4)]ClO_4 ([15]aneN_4=1,4,8,12-tetraazacyclopentadecane; X=F, Cl)$의 전자흡수 스펙트럼을 리간드장 이론으로 해석하였다. AOMX 프로그램을 사용하여 관측한 스핀허용 전이와 계산값을 최적화시켰다. 결정한 CFT 파라미터를 AOM, NSH 및 여러 가지 다른 파라미터와 관련시켜 구하고, 이를 화학적 견지에서 논의하였다. 리간드장 해석으로부터 이들 착물에서는 F 리간드가 강한${\sigma}-$ 및 ${\pi}-$주개인 반면에 Cl 원자는 Cr(III) 이온에 약한 ${\sigma}-$ 및 ${\pi}-$주개 성질이 있음을 확인할 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제26권6호
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• pp.903-908
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• 2005

The sharp-line absorption and emission spectra of $(H_{13}O_6)${$trans-[Cr(Me_2tn)_2Br_2]$}$_2Br_2(ClO_4)\;(Me_2$tn = 2,2-dimethyl-1,3-diaminopropane) have been measured between 13000 $cm^{-1}$ and 16000 $cm^{-1}$ at 5 K. The 298 K infrared and visible absorption spectra have also been measured. The nine electronic bands due to spin-allowed and spin-forbidden transitions were assigned. Using observed transitions, a ligand field analysis has been performed to probe the ligand field properties of coordinated atoms in the title chromium(III) complex ion. The zero-phonon line in the sharp-line absorption spectrum splits into two components by 286 $cm^{-1}$, and the large $^2E_g$ splitting can be reproduced by the modern ligand field theory. It is confirmed that nitrogen atoms of the Me2tn ligand have a strong $\sigma$-donor character, but the bromide has weak $\sigma$- and $\pi$-donor properties toward chromium(III) ion.

• Journal of Photoscience
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• 제3권1호
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• pp.43-47
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• 1996

The 77 K emission and excitation, and room-temperature UV-visible spectra of $\Lambda$-fac[Cr(L-ala)$_3$] (ala = alanine anion) have been measured. The ten electronic transitions due to spinallowed and spin-forbidden are assigned. With the observed electronic transition energies, ligand field optimizations have been performed to determine the bonding properties of L-alanine anion toward chromium(III). The angular overlap model (AOM) parameters obtained indicate that it is electron-donating ligand which has values of e$_{\sigma}O$, e$_{\pi}O$, and e$_{\sigma}N$ slightly lower than those of glycine anion (gly). It seem that the decrease of the ligand field properties is due to steric effect of extra methyl group and inductive effect of adjacent carbonyl group.

• Journal of Photoscience
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• 제7권3호
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• pp.97-101
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• 2000

The 77 K emission and excitation spectra, and 298 K infrared and absorption spectra of mer-[CrCl(en)(dpt)]ZnCl$_4$(en=1,2-diaminoethane; dpt=1,5,9-triazanonane) have been measured. Ligand field electronic transitions due to spin-allowed and spin-forbidden are assigned. The zero-phonon line in the excitation spectrum splits into two components by 151$cm^{-1}$ /, and large$^2$E$^{g}$ splitting can be reproduced by the modern ligand field theory. It is confirmed that nitrogen atoms of the en and dpt ligands have a strong $\delta$-donor character, but chloride ligand has weak $\delta$-and $\pi$-donor properties toward chromium(III) ion.

• Bulletin of the Korean Chemical Society
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• 제20권1호
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• pp.81-84
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• 1999

The emission and excitation spectra of [Cr(NH3)5(imH)](ClO4)3·H2O (imH=imidazole) taken at 77 K are reported. The 298 K visible and far-infrared spectra are also measured. The vibrational intervals of 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 properties of coordinated imidazole in the title chromium(Ⅲ) complex. It is confirmed that nitrogen atom of the imidazole ligand has a medium it-acceptor property toward chromium(Ⅲ) ion. The zero-phonon line in the excitation spectrum splits into two components by 181 cm-1, and the large 2Eg splitting can be reproduced by the ligand field theory.

• Bulletin of the Korean Chemical Society
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• 제18권8호
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• pp.819-823
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• 1997

The luminescence and photoexcitation spectra of cis-[Cr(cyclam)(NO3)2]NO3·½ H2O (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 of 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. With observed transitions, a ligand field analysis has been performed to determine the bonding property of nitrate group in the chromium(Ⅲ) complex. According to the results, it is found that nitrate ligand has weak σ- and π-donor properties toward chromium(Ⅲ).