The Reflection Spectra of Complex Salts of the Tetracyanoquinodimethane Anion Radical

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概要

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• Reflection measurements of the pressed pellets of two 2 : 3 complex salts and six 1 : 2 complex salts of the tetracyanoquinodimethane (TCNQ) anion radical were carried out over the 5000–43000 cm<SUP>−1</SUP> range by the use of Avery's method. The polarized normal-incidence reflection was measured for the Ph<SUB>3</SUB>PCH<SUB>3</SUB>(TCNQ)<SUB>2</SUB>single crystal. The observed results were examined on the basis of the composite-system method. For 2 : 3 salts, the transition energy and the oscillator strength are interpreted by the use of the N-A-A model (N: TCNQ<I><SUP>o</SUP></I> and A-A: TCNQ anion dimer); it is concluded that the interaction between the two components, N and A-A, is weak. In the solid-state spectra of 1 : 2 salts, the assignments were made by the use of the polarization results of the normal-incidence reflection of the Ph<SUB>3</SUB>PCH<SUB>3</SUB>(TCNQ)<SUB>2</SUB> crystal. Besides the four transitions corresponding to those of 2 : 3 salts, two new CT bands with weak intensities were observed and assigned. Except for quinolinium(TCNQ)<SUB>2</SUB>, a spectral change correlative to the electrical conductivity was found in the 1 : 2 salts and discussed in relation to the extent of the delocalization of the negative charge of (TCNQ)<SUB>2</SUB><SUP>−</SUP>. The spectrum of quinolinium(TCNQ)<SUB>2</SUB> exhibits a remarkable intensity decrease compared with those of the other 1 : 2 salts.

• 公益社団法人 日本化学会の論文

著者

• Sakata Tadayoshi

  The Institute for Solid State Physics, The University of Tokyo

• Oohashi Yukako

  The Institute for Solid State Physics, The University of Tokyo

関連論文

• The Reflection Spectra of Simple Salts of the Tetracyanoquinodimethane Anion Radical
• The Reflection Spectra of Complex Salts of the Tetracyanoquinodimethane Anion Radical
• Charge-Transfer Interaction in Linear Chain Molecular Crystals
• Electronic Absorption Spectra and Electronic Structures of Some Würster's Blue Salts
• The Reflection Spectra of Würster's Salts

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