Transition-metal Complexes of Pyrrole Pigments. X. Divalent and Trivalent Manganese Chelates of Dipyrromethenes
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概要
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The solution spectra of two tris(dipyrromethenato)manganese(III) complexes and of one bis(dipyrromethenato) manganese (II) as well as the diffuse reflectance spectrum for the latter were examined. The high spin state was confirmed for all the manganese complexes by magnetic susceptibility measurements. For the tris-complexes, one broad low energy band (∼9500 cm<SUP>−1</SUP>) is assigned to the <SUP>5</SUP>A<SUB>1g</SUB>←<SUP>5</SUP>B<SUB>1g</SUB> transition and one pair of higher energy bands (∼14000 cm<SUP>−1</SUP>) are attributed to the <SUP>5</SUP>B<SUB>2g</SUB>←<SUP>5</SUP>B<SUB>1g</SUB> and <SUP>5</SUP>E<SUB>g</SUB>←<SUP>5</SUP>B<SUB>1g</SUB> transitions for a D<SUB>4h</SUB> symmetry as a consequence of Jahn-Teller effect. In the bis-complex, manganese(II) is placed in a tetrahedral ligand field and one group of ligand-field bands lying below 16000 cm<SUP>−1</SUP> are assigned to: <SUP>4</SUP>T<SUB>1</SUB>(<SUP>4</SUP>G)←<SUP>6</SUP>A<SUB>1</SUB>(<SUP>6</SUP>S), <SUP>4</SUP>T<SUB>2</SUB>(<SUP>4</SUP>G)←<SUP>6</SUP>A<SUB>1</SUB>(<SUP>6</SUP>S), and <SUP>4</SUP>E, <SUP>4</SUP>A<SUB>1</SUB>(<SUP>4</SUP>G)←<SUP>6</SUP>A<SUB>1</SUB>(<SUP>6</SUP>S) in an increasing order of energy. The exceedingly high intensity of these bands is ascribed to the covalent nature of coordinate bonds. A strong IR band due to the skeletal stretching mode of the dipyrromethene moiety was observed in the 1600 cm<SUP>−1</SUP> range and shifted slightly toward lower energy upon metalcoordination.
- 公益社団法人 日本化学会の論文
著者
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Murakami Yukito
Department Of Chemical Science And Technology Faculty Of Engineering Kyushu University
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Sakata Kazunori
Department Of Applied Chemistry Faculty Of Engineering Kyushu Institute Of Technology
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Harada Kenji
Department Of Applied Analysis And Complex Dynamical Systems Kyoto University
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Matsuda Yoshihisa
Department Of Astronomy And Earth Science Tokyo Gakugei University
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