Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Electronic Spectroscopy and Ligand Field Analysis of trans-[CrX2([15]aneN4)]+(X=F,CI)

trans-[CrX2([15]aneN4)]+(X=F,CI)의 전자분광학과 리간드장 해석

  • Jong-Ha Choi (Department of Chemistry, Andong National University) ;
  • In-Gyung Oh (Department of Chemistry, Andong National University) ;
  • Sang Hak Lee (Department of Chemistry, Kyungpook National University) ;
  • Yu Chul Park (Department of Chemistry, Kyungpook National University)
  • 최종하 (안동대학교 자연과학대학 화학과) ;
  • 오인경 (안동대학교 자연과학대학 화학과) ;
  • 이상학 (경북대학교 자연과학대학 화학과) ;
  • 박유철 (경북대학교 자연과학대학 화학과)
  • Published : 2003.04.20
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Abstract

The electronic absorption spectra of trans-$[CrX_2([15]aneN_4)]ClO_4\;([15]aneN_4$=1,4,8,12-tetraazacyclopentadecane; X=F, Cl) complexes have been interpreted using the ligand field theory. An AOMX program is used to optimize the differences between the calculated and the observed positions for the spin-allowed transition bands. The crystal field theory(CFT) parameter is directly related to the angular overlap model(AOM), normalized spherical harmonic hamiltonians(NSH), and semiempirical parameters. The various ligand field parameters are discussed in terms of their chemical significances. According to the ligand field analysis, we can confirm that the fluoride ligand is a very strong ${\sigma}-$ and ${\pi}-$donor while the chloride has weak ${\sigma}-$ and ${\pi}-$donor properties toward chromium(III) ion.

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.

Keywords

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