The Emission Spectra of Hexamminechromium(III) Hexacyanocobaltate(III), [Cr(NH<SUB>3</SUB>)<SUB>6</SUB>][Co(CN)<SUB>6</SUB>]
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概要
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Spin-forbidden absorption bands of K<SUB>3</SUB>[Co(CN)<SUB>6</SUB>] were reexamined employing conventional transmission spectroscopy, diffuse reflectance spectroscopy, and microspectrophotometry. A small but very distinct shoulder (ε≈0.3–0.4) obtained at a low temperature at 26000 cm<SUP>−1</SUP> was assigned to the <SUP>3</SUP>T<SUB>1g</SUB>←<SUP>1</SUP>A<SUB>1g</SUB> transition. Another very small band (ε≈0.001) at 16300 cm<SUP>−1</SUP> was probably due to an impurity. The emission spectra of K<SUB>3</SUB>[Co(CN)<SUB>6</SUB>] powder in the temperature range from room temperature to that of liquid hydrogen were observed by means of a modified Hitachi 203 fluorescence spectrophotometer. The broad emission band at room temperature showed some vibrational structures at low temperatures. The emission spectra of powders of [Cr(NH<SUB>3</SUB>)<SUB>6</SUB>](NO<SUB>3</SUB>)<SUB>3</SUB> and [Cr(NH<SUB>3</SUB>)<SUB>6</SUB>][Co(CN)<SUB>6</SUB>] were also measured. The following results were obtained: i) Similar emission spectra, which seemed to originate from [Cr(NH<SUB>3</SUB>)<SUB>6</SUB>]<SUP>3+</SUP>, were observed with both complexes [Cr(NH<SUB>3</SUB>)<SUB>6</SUB>](NO<SUB>3</SUB>)<SUB>3</SUB> and [Cr-(NH<SUB>3</SUB>)<SUB>6</SUB>][Co(CN)<SUB>6</SUB>] using mercury lines at 313, 365, and 435 nm for excitation, ii) With 254 nm excitation, such emission spectra as i) were not observed with [Cr(NH<SUB>3</SUB>)<SUB>6</SUB>](NO<SUB>3</SUB>)<SUB>3</SUB>, but the same emission spectra as in i) were observed with [Cr(NH<SUB>3</SUB>)<SUB>6</SUB>][Co(CN)<SUB>6</SUB>]. iii) The ratio of the emission intensities at 15000 cm<SUP>−1</SUP> with 435 and 313 nm excitations was 1:0.25–0.30 for [Cr(NH<SUB>3</SUB>)<SUB>6</SUB>](NO<SUB>3</SUB>)<SUB>3</SUB>, but it was 1:1.5–1.7 for [Cr(NH<SUB>3</SUB>)<SUB>6</SUB>][Co(CN)<SUB>6</SUB>]. From these results, it was presumed that, in [Cr(NH<SUB>3</SUB>)<SUB>6</SUB>][Co(CN)<SUB>6</SUB>], there occurred an energy transfer from the complex anion to the complex cation. Furthermore, emission spectra were observed with [Cr(NH<SUB>3</SUB>)<SUB>6</SUB>](ClO<SUB>4</SUB>)<SUB>3</SUB> and the equimolar mixture of complex salts [Cr(NH<SUB>3</SUB>)<SUB>6</SUB>](ClO<SUB>4</SUB>)<SUB>3</SUB>–K<SUB>3</SUB>[Co(CN)<SUB>6</SUB>] and [Cr(NH<SUB>3</SUB>)<SUB>6</SUB>](NO<SUB>3</SUB>)<SUB>3</SUB>–K<SUB>3</SUB>[Co(CN)<SUB>6</SUB>] for the purpose of confirming the energy transfer in [Cr(NH<SUB>3</SUB>)<SUB>6</SUB>][Co(CN)<SUB>6</SUB>]. The temperature dependence of the emission intensity was also discussed.
- 公益社団法人 日本化学会の論文
著者
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KATAOKA Hiroshi
Department of Agricultural Chemistry, The University of Tokyo
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Kataoka Hiroshi
Department of Chemistry, Faculty of Science, Rikkyo University
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