High-field EPR study and crystal and molecular structure of trans-RSSR-[CrCl2n4O(cyclam)]X (X = ZnCl2-, Cl- and Cl-4H2.5HCl)

A Solano-Peralta, M E Sosa-Torres, M Flores-Alamo, H El-Mkami, G M Smith, R A Toscano, T Nakamura

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12 Citations (Scopus)

Abstract

For the first time, HF-EPR (94.5 GHz) spectroscopy has been used to determine crystal field parameters in chromium(III) coordination compounds. The large zero-field splitting parameters of the dark-green photochromic trans-RSSR-[CrCl(2)(2)(4)(2)(2)(2)((cyclam)])(ZnCl)(, 1, the red-purple trans-RSSR-[CrCl)((cyclam)]Cl, 2 and the red-purple trans-RSSR-[CrCl)(-(cyclam)]Cl4H)O0.5HCl, 3, where cyclam = 1,4,8,11-tetraazacyclotetradecane, have been obtained. A full analysis of EPR spectra at 94.5 GHz of diluted complexes 1, 2 and 3 at 300 K revealed that they are extremely sensitive to D and E values. The rhombic distortion was precisely determined for each compound. For 1, g = 2.01, D = -0.305 cm-1, E = 0.041 cm-1 and l E/D = 0.1396; for 2, g = 2.01; D = -0.348 cm-1, E = 0.042 cm-1 and l = E/D = 0.1206 and for 3, g = 1.99, D = -0.320 cm-1, E = 0.041 cm-1 and l = E/D = 0.1281. The EPR study at 94.5 GHz at 10 K allowed us to confirm the sign of the D value for all compounds. These data indicate that at room temperature the crystal field is mainly rhombic and as the temperature decreases, the rhombicity of the D tensor increases slightly. These found differences between 1, 2 and 3 allowed us to establish the importance of the intermolecular interactions in the solid state due to different hydrogen bonding networks in their crystalline arrangement.

Original languageEnglish
Pages (from-to)2444-2449
Number of pages6
JournalDalton Transactions
Issue number16
DOIs
Publication statusPublished - 2004

Keywords

  • ELECTRON-PARAMAGNETIC-RESONANCE
  • HIGH-FREQUENCY EPR
  • SPIN-RESONANCE
  • 1,5,9,13-TETRAAZACYCLOHEXADECANE LIGAND
  • ANGULAR VARIATION
  • COMPLEXES
  • SPECTRA
  • MANGANESE(III)
  • SPECTROSCOPY
  • ABSORPTION

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