Premium
An Uncommon Hypervalent Fluorooxosilicophosphate
Author(s) -
Ding Qingran,
Zhao Sangen,
Xiao Han,
Li Yanqiang,
Liu Shuai,
Li Lina,
Li Chunsen,
Wang Yusong,
Hong Maochun,
Luo Junhua
Publication year - 2019
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201901410
Subject(s) - hypervalent molecule , silicon , crystallography , ion , ionic bonding , conductivity , chemistry , materials science , computational chemistry , organic chemistry , reagent
The species diversity of silicon (including traditional tetrahedral coordinated silicon and hypervalent penta‐ and hexa‐coordinate silicon) gives rise to the structural richness and diverse properties of silicates. Among these silicon species, hypervalent silicon is very rare, not to mention almost unexplored mixed‐anion hypervalent fluoroxosilicate species. In this work, we successfully obtained a mixed‐anion fluorooxosilicophosphate Na4Si2PO4F9 consisting of two uncommon hypervalent fluoroxosilicate species, namely, trans ‐SiO2F4 species and SiOF 5 species. To the best of our knowledge, such hypervalent silicon species are reported for the first time in inorganic compounds. Remarkably, the coexistence of two distinct hypervalent fluoroxosilicate species in one compound is somewhat conflicted with Pauling's parsimony rule, but it indeed achieves an unlikely connection by PO 4 and our phonon dispersion calculation confirms the structure stability of Na 4 Si 2 PO 4 F 9 . Temperature‐dependent conductivity measurements show that Na 4 Si 2 PO 4 F 9 is a promising solid ionic conductor with a high conductivity of 4.0×10 −5 S⋅cm −1 at 700 K and a low active energy of about 53.1 KJ⋅mol −1 . This work will enrich the structure chemistry of silicates and may provide a new platform for solid ionic batteries.