Photoemission and Excitation Spectroscopy of cis-Difluoro(1,4,8,11-Tetraazacyclotetradecane) Chromium (III) Perchlorate

  • Published : 2000.03.01

Abstract

The photoemission and excitation spectra of cis-[Cr(cyclam)F$_2$]ClO$_4$ (cyclam = 1,4,8,11-tetraazacy-clotetradecane) taken at 77 K are reported. The 298 K mid- 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. The zero-phonon line In the excitation spectrum splits into two components by 169 cm$^{1}$, and the large $^2$E$_{g}$ splitting can be reproduced by the ligand field theory. According to the ligand field analysis, we can confirm that nitrogen atoms of the cyclam ligand have a strong c-donor character, and fluoride ligand also has strong $\sigma$- and $\pi$-donor properties toward chromium(III) ion.n.

Keywords

References

  1. Physics of Solid-State Laser Materials Powell,R.C.
  2. Crystal Fields for Transition-Metal Ions in Laser Host Materials Morrison,C.A.
  3. Top. Curr. Chem. v.171 Sharp line electronic spectra and metal ligand geometry Hoggard,P.E.
  4. J. Photosci. v.3 Electronic spectroscopy and lignad field analysis of Λ-fac-tris(L-alaninato)chromium(Ⅲ) Choi,J.H.
  5. Bull. Korean Chem. Soc. v.18 Sharp-line electronic spectroscopy and ligand field analysis of [Cr(transdiammac)](CIO₄)₃ Choi,J.H.;I.G.Oh
  6. Top. Curr. Chem. v.191 Angular overlap model applied to transition metal complexes and dN-ions in oxide host lattices Schonherr,T.
  7. Bull. Korean Chem. Soc. v.19 Luminescence, excitation and far-infrared spectroscopy of cis-α-dichlorotriethyleneteraminechromium(Ⅲ) Chloride Choi,J.H.
  8. Bull. Korean Chem. Soc. v.20 Spectroscopic properties and ligand field analysis of pentaammine(imidazole)chromium(Ⅲ) perchlorate Choi,J.H.
  9. Bull. Korean Chem. Soc. v.20 High resolution optical spectroscopy of mer-[Cr(dpt) (Gly-Gly)]CIO₄ Choi,J.H.
  10. Bull. Korean Chem. Soc. v.15 Spectroscopic properties and lignad field analysis of tris(trans-1,2-cyclohexanediamine)chromium(Ⅲ) chloride Choi,J.H.
  11. Goord. Chem. Rev. v.70 Sharp line electronic transitions and metal-ligand angular geometry Hoggard,P.E.
  12. Inorg. Chem. v.25 Synthesis, Characterization, and Photobehavior of Macrocyclic Difluoro Complexes of Chromium(Ⅲ) Kane-Maguire,N.A.P.;K.C.Wallace;D.G.Speece
  13. J. Phys. Chem. v.90 Low-Temperature Luminescence of Chromium(Ⅲ) Complexes Coordinated With Macrocyclic Tetraamine Ligands Forster,L.S.;O.Monsted
  14. Infrared and Raman Spectra of Inorganic and Coordination Compounds(5th Ed.) Nakamoto,K.
  15. Chem. Phys. v.256 Spectral properties and ligand field analysis of cis-Dinitrito(1,4,8,11-tetraazacyclotetradecane)chromium(Ⅲ) Azide Choi,J.H.
  16. Bull. Kor. Chem. Soc. v.14 Sharp line electronic spectroscopy and ligand field analysis of cis-(1,4,8,11-tetraazacyclotetradecane)*ethylenediamine)chromium(Ⅲ) Choi,J.H.;I.G.Oh
  17. Bull. Korean Chem. Soc. v.14 Spectroscopic properties of cis-(1,4,8,11-tetraaza cyclotetradecane)(1,2-propanediamine)chromium(Ⅲ) Choi,J.H.
  18. J. Kor. Chem. Soc. v.39 A spectroscopic study on the electronic structure of cis-[Cr(cyclam)Cl ₂]Cl Choi,J.H.
  19. J. Photosci. v.4 Optical spectroscopy and ligand field parameters of cis-dibromo(1,4,8,11-tetraazacyclotetradecane)chromium(Ⅲ) Bromide Choi,J.H.
  20. Spectrochim. Acta v.56A Spectroscopic properties and ligand field analysis of cis-Diazido(1,4,8,11-tetraazacyclotetradecane)chromium(Ⅲ) Azide Choi,J.H.
  21. Bull. Korean Chem. Soc. v.18 Spectroscopic properties and ligand field analysis of cis-Dinitrato(1,4,8,11-tetraazacyclotetradecane)chromium(Ⅲ) Nitrate Choi,J.H.
  22. Inorganic Electronic Spectroscopy Lever,A.B.P.
  23. Ligand field Theory and its Applications Figgis,B.N.;M.A.Hitchman
  24. Matrix Eigensystem Routines-EISPACK Guide Smith,B.T.;J.M.Boyle;J.J.Dongarra;B.S.Garbow;Y.Ikebe;V.C.Klema;C.B.Moler
  25. Phys. Rev. v.83 Configuration interaction in Mn(Ⅱ) Trees,R.E.
  26. Polyhedron v.11 Ligand field properties of the peptide nitrogen: The sharp line electronic spectrum of mer-di(3-aminopropyl)amine(glycylglycinato-O,N,N')chromium(Ⅲ) Choi,J.H.;P.E.Hoggard
  27. Optimization Techniques with Fortran Kuester,J.L.;J.H.Mize
  28. Multivariate Error Analysis Clifford,A.A.
  29. Coord. Chem. Rev. v.48 Ligand field model of and the photochemistry of coordination compounds Vanquickenborne,L.G.;A.Ceulemans