We found a match
Your institution may have rights to this item. Sign in to continue.
- Title
Formation of Mixed‐Valence Luminescent Silver Clusters via Cation‐Coupled Electron‐Transfer in a Redox‐Active Ionic Crystal Based on a Dawson‐type Polyoxometalate with Closed Pores.
- Authors
Haraguchi, Naoya; Okunaga, Tomoki; Shimoyama, Yuto; Ogiwara, Naoki; Kikkawa, Soichi; Yamazoe, Seiji; Inada, Miki; Tachikawa, Takashi; Uchida, Sayaka
- Abstract
A redox‐active ionic crystal based on a Dawson‐type polyoxometalate (POM) [α‐P2WVI18O62]6− is utilized to form and stabilize small mixed‐valence luminescent silver clusters without the aid of protecting ligands at room temperature. A reduced ionic crystal of Cs3H5[Cr3O(OOCH)6(etpy)3]3[α‐P2WV5WVI13O62] ⋅ 5H2O (etpy=4‐ethylpyridine) is formed by a cation‐coupled electron‐transfer (CCET) reaction with sodium ascorbate as a reducing reagent to provide electrons and Cs+ as counter cations of POM. Then, silver is introduced via ion‐exchange between Cs+ and Ag+ jointly with CCET reaction: X‐ray photoelectron spectroscopy and elemental analysis show that the ionic crystal is oxidized via electron‐transfer from the POM (W5+) to Ag+, and [Ag01.5AgI1.5]H4.5[Cr3O(OOCH)6(etpy)3]3[α‐P2WV3WVI15O62] ⋅ 7H2O is formed. Photoluminescence and X‐ray absorption fine structure suggest that the silver species exist as mixed‐valence luminescent clusters with an average formula of [Ag4]2+ probably in a tetrahedral geometry.
- Subjects
SILVER clusters; IONIC crystals; X-ray photoelectron spectroscopy; X-ray absorption near edge structure; VITAMIN C; X-ray absorption
- Publication
European Journal of Inorganic Chemistry, 2021, Vol 2021, Issue 16, p1531
- ISSN
1434-1948
- Publication type
Article
- DOI
10.1002/ejic.202100101