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タイトル: Interest in new heterodinuclear transition-metal/main-group-metal complexes: DFT study of electronic structure and mechanism of fluoride sensing function.
著者: Guan, Wei
Yamabe, Shinichi
Sakaki, Shigeyoshi
著者名の別形: 榊, 茂好
発行日: 28-Jun-2013
出版者: Royal Society of Chemistry
誌名: Dalton transactions
巻: 42
号: 24
開始ページ: 8717
終了ページ: 8728
抄録: Systematic DFT calculations were carried out on a series of heterodinuclear complexes [(o-(Ph2P)C6H4)3M(1)M(2)Cl](+) (M(1) = As, Sb, or Bi; M(2) = Pd or Pt) to investigate the mechanism of colorimetric sensing function for the fluoride anion. The fluoride anion binds with the M(1) center to afford a hypervalent M(1) species with large stabilization energy. For instance, the stabilization energy by the fluoride adduct formation is -15.5 kcal mol(-1) for 3 (M(1) = Sb; M(2) = Pd) and -16.2 kcal mol(-1) for 6 (M(1) = Sb; M(2) = Pt), where a negative value represents stabilization. Interestingly, the allosteric coordination of the third phosphine with the M(2) center is induced by the fluoride adduct formation. For chloride, bromide, and thiocyanide anions, the binding energies are positive (~4.5 kcal mol(-1)), and the allosteric coordination does not occur. The allosteric coordination plays a crucial role in the absorption spectrum change induced by the fluoride adduct formation. For instance, the fluoride adduct formation quenches the absorption band of 3 around 400 nm and newly exhibits two absorption peaks at longer wavelength, 475 and 451 nm. These two peaks are assigned to ligand-field transitions (d(xy)→ d(z(2)) and d(x(2)-y(2))→ d(z(2))) including metal-to-ligand charge transfer character. We discussed the reasons why the allosteric coordination can occur only in the fluoride adduct and induces these two absorptions in the longer wavelength region. In addition, the Bi-Pd combination is also recommended for a fluoride sensing material, while the Sb-Pt combination is recommended for cyanide sensing.
著作権等: This journal is © The Royal Society of Chemistry 2013
This is not the published version. Please cite only the published version. この論文は出版社版でありません。引用の際には出版社版をご確認ご利用ください。
URI: http://hdl.handle.net/2433/189887
DOI(出版社版): 10.1039/c3dt50597a
PubMed ID: 23632755
出現コレクション:学術雑誌掲載論文等

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