An Air-Synthesized, Mixed-Valent Vanadium Tungsten Monophosphate with Intersecting Tunnels: Cs5VW4O9VO4(PO4)4

✍ Scribed by F Berrah; A Leclaire; A Guesdon; M.M Borel; J Provost; B Raveau

• Book ID: 102606065
• Publisher: Elsevier Science
• Year: 1998
• Tongue: English
• Weight: 470 KB
• Volume: 141
• Category: Article
• ISSN: 0022-4596
• DOI: 10.1006/jssc.1998.7935

✦ Synopsis

A new mixed-valent vanadium tungsten monophosphate Cs 5 V 2 W 4 O 13 (PO 4 ) 4 has been synthesized in air in spite of the presence of V(IV). It crystallizes in the space group Cmc2 1 with a ‫؍‬ 14.948(1), b ‫؍‬ 20.008(2), and c ‫؍‬ 9.942(1) A s . Its original structure, built up from W 2 O 11 bioctahedra, P 2 VO 10 tritetrahedra units, and VO 5 pyramids, can be described from [W 2 P 2 O 13 ] layers parallel to (100) interconnected through VO 4 tetrahedra and VO 5 pyramids. This open framework forms intersecting tunnels running along al and cl , where the Cs ؉ cations are located. Bond strength-bond length calculations and magnetic measurements show that the electrons are localized, V(IV) sitting in the VO 5 pyramid, whereas the VO 4 tetrahedra and WO 6 octahedra are occupied by V(V) and W(VI), respectively.