TY  - JOUR
AU  - Bykov, Maxim
AU  - Bykova, Elena
AU  - Hanfland, Michael
AU  - Liermann, Hanns-Peter
AU  - Kremer, Reinhard K.
AU  - Glaum, Robert
AU  - Dubrovinsky, Leonid
AU  - van Smaalen, Sander
TI  - High-Pressure Phase Transformations in TiPO<sub>4</sub>: A Route to Pentacoordinated Phosphorus
JO  - Angewandte Chemie / International edition
VL  - 55
IS  - 48
SN  - 1433-7851
CY  - Weinheim
PB  - Wiley-VCH
M1  - PUBDB-2016-05328
SP  - 15053 - 15057
PY  - 2016
N1  - (c) Wiley-VCH Verlag GmbH & Co. Post referee full text in progress (embargo 1 year from 31 OCT 2016).
AB  - 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.
LB  - PUB:(DE-HGF)16
UR  - <Go to ISI:>//WOS:000388258000028
C6  - pmid:27798821
DO  - DOI:10.1002/anie.201608530
UR  - https://bib-pubdb1.desy.de/record/312139
ER  -