학술논문
Factors governing the protonation of Keggin-type polyoxometalates: influence of the core structure in clusters.
Document Type
Academic Journal
Author
Sampei H; Department of Applied Chemistry, Waseda University, 3-4-1, Okubo, Shinjuku, Tokyo, 169-8555, Japan. ysekine@waseda.jp.; Akiyama H; Department of Applied Chemistry, Waseda University, 3-4-1, Okubo, Shinjuku, Tokyo, 169-8555, Japan. ysekine@waseda.jp.; Saegusa K; Department of Applied Chemistry, Waseda University, 3-4-1, Okubo, Shinjuku, Tokyo, 169-8555, Japan. ysekine@waseda.jp.; Yamaguchi M; Department of Applied Chemistry, Waseda University, 3-4-1, Okubo, Shinjuku, Tokyo, 169-8555, Japan. ysekine@waseda.jp.; Ogo S; Department of Marine Resource Science, Faculty of Agriculture and Marine Science, Kochi University, Nankoku 783-8502, Japan.; Marine Core Research Institute, Kochi University, Nankoku 783-8502, Japan.; Nakai H; Department of Chemistry and Biochemistry, Waseda University, 3-4-1, Okubo, Shinjuku, Tokyo, 169-8555, Japan.; Ueda T; Department of Marine Resource Science, Faculty of Agriculture and Marine Science, Kochi University, Nankoku 783-8502, Japan.; Marine Core Research Institute, Kochi University, Nankoku 783-8502, Japan.; MEDi Center, Kochi University, Kochi 780-0842, Japan.; Sekine Y; Department of Applied Chemistry, Waseda University, 3-4-1, Okubo, Shinjuku, Tokyo, 169-8555, Japan. ysekine@waseda.jp.
Source
Publisher: Royal Society of Chemistry Country of Publication: England NLM ID: 101176026 Publication Model: Electronic Cited Medium: Internet ISSN: 1477-9234 (Electronic) Linking ISSN: 14779226 NLM ISO Abbreviation: Dalton Trans Subsets: PubMed not MEDLINE; MEDLINE
Subject
Language
English
Abstract
Atomic substitution is a promising approach for controlling structures and properties for developing clusters with desired responses. Although many possible coordination candidates could be deduced for substitution, not all can be prepared. Therefore, predicting the correlation between structures and physical properties is important prior to synthesis. In this study, regarding Keggin-type polyoxometalates (POMs) as a model cluster, the dominant factors affecting the protonation were investigated by atomic substitutions and geometry changes. The valence of Keggin-type POMs and the constituent elements of the cluster shell structure affect the charge and potential distribution, which change the protonation sites. Furthermore, the valence of Keggin-type POMs and the bond length between the core and shell structure determine the protonation energy. These factors also affect the HOMO-LUMO gap, which governs photochemical and redox reactions. These governing factors derived from actual parameters of the α-isomer of Keggin-type POMs enabled us to deduce the protonation energy of the β-isomer, which is more difficult to prepare and isolate than the α-isomer.