%0 Journal Article
%A Bykov, Maxim
%A Bykova, Elena
%A Hanfland, Michael
%A Liermann, Hanns-Peter
%A Kremer, Reinhard K.
%A Glaum, Robert
%A Dubrovinsky, Leonid
%A van Smaalen, Sander
%T High-Pressure Phase Transformations in TiPO<sub>4</sub>: A Route to Pentacoordinated Phosphorus
%J Angewandte Chemie / International edition
%V 55
%N 48
%@ 1433-7851
%C Weinheim
%I Wiley-VCH
%M PUBDB-2016-05328
%P 15053 - 15057
%D 2016
%Z (c) Wiley-VCH Verlag GmbH & Co. Post referee full text in progress (embargo 1 year from 31 OCT 2016).
%X Titanium(III) phosphate, TiPO<sub>4</sub> , is a typical example of an oxyphosphorus compound containing covalent P−O bonds. Single-crystal X-ray diffraction studies of TiPO<sub>4</sub> reveal complex and unexpected structural and chemical behavior as a function of pressure at room temperature. A series of phase transitions lead to the high-pressure phase V, which is stable above 46 GPa and features an unusual oxygen coordination of the phosphorus atoms. TiPO<sub>4</sub>-V is the first inorganic phosphorus-containing compound that exhibits fivefold coordination with oxygen. Up to the highest studied pressure of 56 GPa, TiPO<sub>4</sub>-V coexists with TiPO<sub>4</sub>-IV, which is less dense and might be kinetically stabilized. Above a pressure of about 6 GPa, TiPO<sub>4</sub>-II is found to be an incommensurately modulated phase whereas a lock-in transition at about 7 GPa leads to TiPO<sub>4</sub>-III with a fourfold superstructure compared to the structure of TiPO<sub>4</sub>-I at ambient conditions. TiPO<sub>4</sub>-II and TiPO<sub>4</sub>-III are similar to the corresponding low-temperature incommensurate and commensurate magnetic phases and reflect the strong pressure dependence of the spin-Peierls interactions.
%F PUB:(DE-HGF)16
%9 Journal Article
%U <Go to ISI:>//WOS:000388258000028
%$ pmid:27798821
%R 10.1002/anie.201608530
%U https://bib-pubdb1.desy.de/record/312139