Copper(II)-lanthanoid(III) complexes of binucleating ligands derived from 3-formylsalicylic acid and diamines.
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概要
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Heterometal binuclear complexes, [CuLn(fsaen)(H<SUB>2</SUB>O)<I><SUB>n</SUB></I>](NO<SUB>3</SUB>) (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu; <I>n</I>=4–5) and [CuLn(fsapn)(H<SUB>2</SUB>O)<SUB>4</SUB>](NO<SUB>3</SUB>) (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, or Dy) have been synthesized and characterized, where H<SUB>4</SUB>fsaen and H<SUB>4</SUB>fsapn denote <I>N</I>,<I>N</I>′-bis(3-carboxysalicylidene)ethylenediamine and <I>N</I>,<I>N</I>′-bis(3-carboxysalicylidene)-1,2-propanediamine, respectively. The ligand field band due to the copper(II) ion bound to the N<SUB>2</SUB>O<SUB>2</SUB>-site is at 18.5×10<SUP>3</SUP>–19.5×10<SUP>3</SUP> cm<SUP>−1</SUP> for [CuLn(fsaen)(H<SUB>2</SUB>O)<I><SUB>n</SUB></I>](NO<SUB>3</SUB>) and 18.4×10<SUP>3</SUP>–19.2×10<SUP>3</SUP> cm<SUP>−1</SUP> for [CuLn(fsapn)(H<SUB>2</SUB>O)<SUB>4</SUB>](NO<SUB>3</SUB>), which are higher frequencies than those of the mononuclear complexes, [Cu(H<SUB>2</SUB>fsaen)](H<SUB>2</SUB>O)<SUB>0.5</SUB> and [Cu(H<SUB>2</SUB>fsapn)](H<SUB>2</SUB>O)<SUB>0.5</SUB> (18.3×10<SUP>3</SUP> and 18.4×10<SUP>3</SUP> cm<SUP>−1</SUP>, respectively). When the complexes are dissolved in pyridine (Py), dimethyl sulfoxide (DMSO), or <I>N</I>,<I>N</I>-dimethylformamide (DMF), the d–d band frequency decreases in the order of the solvent DMSO>DMF>Py for the binuclear complexes, whereas it decreases in the order of DMF>DMSO>Py for the mononuclear complexes. These trends were discussed in terms of the different affinities of solvent molecules for copper(II) and lanthanoid(III) ions. No significant magnetic spin-exchange interaction occurred between metal ions.
- 公益社団法人 日本化学会の論文
著者
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Okawa Hisashi
Department Of Chemistry Faculty Of Science Kyushu University
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Takagi Minoru
Department Of Anatomy Dental Research Center Nihon University School Of Dentistry
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SAKAMOTO Masatomi
Department of Applied Chemistry, Faculty of Engineering, Ehime University
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Ishimori Tomitaro
Department of Industrial Chemistry, Faculty of Engineering, Ehime University
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SAKAMOTO Masatomi
Department of Industrial Chemistry, Faculty of Engineering, Ehime University
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