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| Home > Publications database > High-Pressure Phase Transformations in $\mathrm{TiPO_{4}}$: A Route to Pentacoordinated Phosphorus |
| Home > Publications database > High-Pressure Phase Transformations in $\mathrm{TiPO_{4}}$: A Route to Pentacoordinated Phosphorus |
| Journal Article | PUBDB-2016-05328 |
; ; ; ; ; ; ;
2016
Wiley-VCH
Weinheim
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Please use a persistent id in citations: doi:10.1002/anie.201608530
Abstract: Titanium(III) phosphate, TiPO$_4$ , is a typical example of an oxyphosphorus compound containing covalent P−O bonds. Single-crystal X-ray diffraction studies of TiPO$_4$ 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$_4$-V is the first inorganic phosphorus-containing compound that exhibits fivefold coordination with oxygen. Up to the highest studied pressure of 56 GPa, TiPO$_4$-V coexists with TiPO$_4$-IV, which is less dense and might be kinetically stabilized. Above a pressure of about 6 GPa, TiPO$_4$-II is found to be an incommensurately modulated phase whereas a lock-in transition at about 7 GPa leads to TiPO$_4$-III with a fourfold superstructure compared to the structure of TiPO$_4$-I at ambient conditions. TiPO$_4$-II and TiPO$_4$-III are similar to the corresponding low-temperature incommensurate and commensurate magnetic phases and reflect the strong pressure dependence of the spin-Peierls interactions.
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