Oxyphosphides Explained

Oxyphosphides are chemical compounds formally containing the group PO, with one phosphorus and one oxygen atom. The phosphorus and oxygen are not bound together as in phosphates or phosphine oxides, instead they are bound separately to the cations (metals), and could be considered as a mixed phosphide-oxide compound. So a compound with O_mP_n requires cations to balance a negative charge of 2m+3n. The cations will have charges of +2 or +3. The trications are often rare earth elements or actinides. They are in the category of oxy-pnictide compounds.

Many compounds are layered, containing two metals with the formula XZPO, with an XP layer alternating with a ZO layer.

Examples

Examples include

• Ca₄P₂O greenish gold, has space group I4mmm Z=2 and unit cell parameters a = 4.492, c = 15.087.^[1]
• Uranium–Copper Oxyphosphide UCuPO semimetallic antiferromagnetic tetragonal ZrCuSiAs-type a =3:7958 c=8:2456 V=118.80 Z=2 MW=348.55 density=9.743^[2]
• Thorium–Copper Oxyphosphide ThCuPO semimetallic tetragonal ZrCuSiAs-type a=3.8995 c=8.2939 V=126.12 Z=2 MW=342.56 density=9.02.^[2]
• NpCuOP^[3]
• Sr₂ScCoPO₃ high thermoelectric effect^[4]
• Sr₂ScFePO₃ superconducting 17K.^{[4] [5]}
• LaNiOP Lanthanum nickel oxyphosphide^[6]
• YOFeP^[7]
• YOMnP^[7]
• YOCdP^[7]
• ROTPn (R = La, Nd, Sm, Gd; T = Mn, Fe, Co, Ni, Cu; Pn = P, As, Sb) ^[8]
• YZnPO transparent red Rm Z=6 a = 3.946, c = 30.71^[9]
• LaZnPO transparent red ZrCuSiAs type^[9]
• DyZnPO transparent red Rm Z=6 a=3.8933 c=30.305^[9]
• PrZnPO transparent red dimorphic ^[9]
• SmZnPO transparent red Rm Z=6 a = 3.946, c = 30.71^[9]
• NdZnPO transparent a = 3.885 c = 30.32^[9]
• GdZnPO transparent red Rm Z=6 a=3.922, c = 30.56^[9]
• CeZnPO transparent^[9]
• HoZnPO transparent dark red^[9]
• CeRuPO ferromagnetic below 15K. dimorphic^[9]
• CeOsPO antiferromagnetic^[9]

related phosphide oxides

• La₂AuP₂O C2/m, a=15.373 b=4.274 c=10.092 β=131.02 V=500.3 dark-red-violet^[10]
• Ce₂AuP₂O C2/m, a = 15.152, b = 4.2463, c = 9.992 pm, β = 130.90° dark-red-violet ^[10]
• Pr₂AuP₂O C2/m, a = 15.036, b = 4.228, c = 9.930 pm, β = 130.88(2)° dark-red-violet ^[10]
• Nd₂AuP₂O C2/m, a = 15.0187, b = 4.2085, c = 9.903 pm, β = 131.12(1)° dark-red-violet ^[10]

Oxy-pnictides

Related compounds are the oxybismuthides^[11] and oxyarsenides.

Notes and References

1. Hadenfeldt . C . Vollert . H.O . Darstellung und kristallstruktur der calciumpnictidoxide Ca4P2O und Ca4As2O . Journal of the Less Common Metals . December 1988 . 144 . 2 . 143–151 . 10.1016/0022-5088(88)90126-9.
2. Sakai. Hironori. Tateiwa. Naoyuki. D. Matsuda. Tatsuma. Sugai. Takashi. Yamamoto. Etsuji. Haga. Yoshinori. Crystal Structure and Physical Properties of Uranium–Copper Oxyphosphide UCuPO. Journal of the Physical Society of Japan. 15 July 2010. 79. 7. 074721. 10.1143/JPSJ.79.074721. 2010JPSJ...79g4721H.
3. Wells. Daniel M.. Ringe. Emilie. Kaczorowski. D.. Gnida. D.. André. G.. Haire. Richard G.. Ellis. Donald E.. Ibers. James A.. Structure, Properties, and Theoretical Electronic Structure of UCuOP and NpCuOP. Inorganic Chemistry. 17 January 2011. 50. 2. 576–589. 10.1021/ic101665g. 21158457.
4. has layers of CoP alternating with Sr₂ScO₃.Okada. S. Kamihara. Y. Ohkubo. N. Ban. S. Matoba. M. Atou. T. Physical properties of the novel layered cobalt oxyphosphide Sr2ScCoPO3. Journal of Physics: Conference Series. 17 December 2012. 400. 2. 022091. 10.1088/1742-6596/400/2/022091. 2012JPhCS.400b2091O. free.
5. Ogino. Hiraku. Matsumura. Yutaka. Katsura. Yukari. Ushiyama. Koichi. Horii. Shigeru. Kishio. Kohji. Shimoyama. Jun-ichi. Superconductivity at 17 K in (Fe2P2)(Sr4Sc2O6): a new superconducting layered pnictide oxide with a thick perovskite oxide layer. Superconductor Science and Technology. 1 July 2009. 22. 7. 075008. 10.1088/0953-2048/22/7/075008. 2009SuScT..22g5008O. 0903.3314. 118525802.
6. Watanabe. Takumi. Yanagi. Hiroshi. Kamiya. Toshio. Kamihara. Yoichi. Hiramatsu. Hidenori. Hirano. Masahiro. Hosono. Hideo. Nickel-Based Oxyphosphide Superconductor with a Layered Crystal Structure, LaNiOP. Inorganic Chemistry. September 2007. 46. 19. 7719–7721. 10.1021/ic701200e. 17705374.
7. Web site: Moreau. Meghann A.. Flux Synthesis and Characterization of Layered Oxyphosphides in the YOMP System (M=Fe, Mn, Cd). The 7th Annual NC State University Undergraduate Summer Research Symposium. 16 January 2017.
8. Pressure Effects on the Superconducting and Spin-Density-Wave States of the Newly Discovered Sm(O1-XFX)FeAs. 0804.1582v1. Lorenz. B.. Sasmal. K.. Chaudhury. R. P.. Chen. X. H.. Liu. R. H.. Wu. T.. Chu. C. W.. 2008. cond-mat.supr-con.
9. Lincke. Hannes. Glaum. Robert. Dittrich. Volker. Tegel. Marcus. Johrendt. Dirk. Hermes. Wilfried. Möller. Manfred H.. Nilges. Tom. Pöttgen. Rainer. Magnetic, Optical, and Electronic Properties of the Phosphide OxidesREZnPO (RE = Y, La–Nd, Sm, Gd, Dy, Ho). Zeitschrift für anorganische und allgemeine Chemie. July 2008. 634. 8. 1339–1348. 10.1002/zaac.200800066.
10. Bartsch. Timo. Wiegand. Thomas. Ren. Jinjun. Eckert. Hellmut. Johrendt. Dirk. Niehaus. Oliver. Eul. Matthias. Pöttgen. Rainer. Phosphide Oxides M2AuP2O (M= La, Ce, Pr, Nd): Synthesis, Structure, Chemical Bonding, Magnetism, and 31P and 131La Solid State NMR. Inorganic Chemistry. 18 February 2013. 52. 4. 2094–2102. 10.1021/ic302475u. 23374070.
11. Kozhevnikov. V. L.. Leonidova. O. N.. Ivanovskii. A. L.. Shein. I. R.. Goshchitskii. B. N.. Kar’kin. A. E.. New superconductor with a layered crystal structure: Nickel oxybismuthide LaO1−δNiBi. JETP Letters. 5 February 2009. 87. 11. 649–651. 10.1134/S002136400811012X. 2008JETPL..87..649K. 120451483.