Phosphidogermanate

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Phosphidogermanates are chemical compounds that have phosphorus bound to germanium to yield anions. They are in the category of phosphidotetrelates and also pnictides. They are analogous to nitridogermanates, phosphidoaluminates, phosphidogallates, phosphidoindates, phosphidosilicates or phosphidostannates.

They are under investigation as infrared non-linear optic materials [1] and solid-state electrolytes. [2]

List

formulaMWcrystal

system

space

group

unit cell Åvolumedensityformpropertiesreferences
GePmonoclinicC2/ma = 15.1948 b = 3.6337 c = 9.1941 β = 101.239° [3]
Li2GeP2148.458tetragonalI41/acda = 12.3069 c = 19.0306 Z=322882.422.736Ge4P10 supratetrahedrared [4]
LiGe3P3317.751orthorhombicPbama = 9.8459 b = 15.7489 c = 3.5995 Z=4558.153.780GeP4 and Ge(P3Ge) tetrahedra in

5 and 6-membered rings making 2D slabs

black [4]
Li8GeP4252Pa3a=11.80203 c=11.80203 Z=81643.882.037 [5] [6]
Li8GeP4251.99cubicP43na=11.77294 Z=81635.982.046 [5] [6]
Li14GeP6cubicFm3ma=5.95667 Z=41.860brown [2] [7]
Li10.1Ge5PPnmaa=10.360 b=4.3072 c=24.267 Z=41082.82.86Ge5 ringsblack; actually is a germanide phosphide [8]
NaGe3P3orthorhombicPmc21a=3.6276 b=8.407 c=10.332 Z=2315.093.517Ge3P7 ringred; band gap 2.06 eV; semiconductor [9]
Na2Ge3P3356.72monoclinicC2/ma = 17.639 b = 3.6176 c = 11.354 β = 92.74° Z=4723.73.274black [10]
Na3Ge2P3307.06monoclinicP21/ca = 7.2894 b = 14.7725 c = 7.0528 β = 106.331° Z=4728.82.798Ge2P6 with shared Pblack [11]
Na5Ge7P5monoclinicC2/ma = 16.168 b = 3.6776 c = 12.924 β = 91.30° Z=2768.23.343black [10]
Na8GeP4380.4cubicFd3ma=13.4230 Z=82418.532.08943same as Na8SnSb4black; decomposes over 350°C to Na10Ge2P6;band gap 1.9 eV [5]
Na10Ge2P6monoclinicP21/na=13.176 b =7.36.4 c=8.042 β=90.26° Z=2780.292.38beige; moisture sensitive [12]
CuGe2P3 [13]
ZnGeP2I42da=5.466 c=10.722melt 1027°C [1] [14] [15] [16]
Ag6Ge10P121744.76cubicI43ma=10.3111 Z=21096.35.286air stable; silver grey; thermoelectric [17] [18] [19]
CdGeP2I42da=5.740 c=10.773 [20]
Cs5GeP3orthorhombicPnmaa=14.31 b=5.994 c=15.618 Z=4metallic [21]
BaGe2P2344.46tetragonalP42mca =7.6153 c =8.490 Z=4492.34.647light metallic grey; melt 861 °C [22]

References

  1. 1 2 Yang, He-Di; Ran, Mao-Yin; Wei, Wen-Bo; Wu, Xin-Tao; Lin, Hua; Zhu, Qi-Long (2021-11-02). "The Rise of Infrared Nonlinear Optical Pnictides: Advances and Outlooks" . Chemistry: An Asian Journal. 16 (21): 3299–3310. doi:10.1002/asia.202100935. ISSN   1861-4728. PMID   34469055. S2CID   237372337.
  2. 1 2 Strangmueller, Stefan; Eickhoff, Henrik; Mueller, David; Klein, Wilhelm; Raudaschl-Sieber, Gabriele; Kirchhain, Holger; Sedlmeier, Christian; Baran, Volodymyr; Senyshyn, Anatolyi; Deringer, Volker L.; van Wüllen, Leo; Gasteiger, Hubert A.; Fässler, Thomas Friedrich (2020-11-23). "Fast Lithium Ionic Conductors Li 14 SiP 6 , Li 14 GeP 6 , and Li 14 SnP 6 – Structure-Property-Relationships in the Newly Discovered Family of Lithium Phosphidotetrelates" . ECS Meeting Abstracts. MA2020-02 (5): 874. doi:10.1149/MA2020-025874mtgabs. ISSN   2151-2043. S2CID   234511163.
  3. Shen, Hailin; Ma, Zhongtao; Yang, Bingchao; Guo, Bingkun; Lyu, Yingchun; Wang, Peng; Yang, Hangsheng; Li, Qianqian; Wang, Hongtao; Liu, Zhongyuan; Nie, Anmin (September 2019). "Sodium storage mechanism and electrochemical performance of layered GeP as anode for sodium ion batteries" . Journal of Power Sources. 433: 126682. Bibcode:2019JPS...43326682S. doi:10.1016/j.jpowsour.2019.05.088. S2CID   195416712.
  4. 1 2 Eickhoff, Henrik; Sedlmeier, Christian; Klein, Wilhelm; Raudaschl-Sieber, Gabriele; Gasteiger, Hubert A.; Fässler, Thomas F. (2020-02-14). "Polyanionic Frameworks in the Lithium Phosphidogermanates Li 2 GeP 2 and LiGe 3 P 3 – Synthesis, Structure, and Lithium Ion Mobility". Zeitschrift für anorganische und allgemeine Chemie. 646 (3): 95–102. doi: 10.1002/zaac.201900228 . ISSN   0044-2313. S2CID   214226863.
  5. 1 2 3 Fässler, Thomas Friedrich; Botta, Manuel; Zeitz, Sabine (2023-08-31). "Synthesis, Structure and Physical Properties of the Most Sodium-Rich Phosphidogermanate Na8GeP4". Zeitschrift für anorganische und allgemeine Chemie. doi: 10.1002/zaac.202300166 . ISSN   0044-2313.
  6. 1 2 Eickhoff, Henrik; Strangmüller, Stefan; Klein, Wilhelm; Kirchhain, Holger; Dietrich, Christian; Zeier, Wolfgang G.; van Wüllen, Leo; Fässler, Thomas F. (2018-09-25). "Lithium Phosphidogermanates α- and β-Li 8 GeP 4 —A Novel Compound Class with Mixed Li + Ionic and Electronic Conductivity" . Chemistry of Materials. 30 (18): 6440–6448. doi:10.1021/acs.chemmater.8b02759. ISSN   0897-4756. S2CID   106211828.
  7. Strangmüller, Stefan; Eickhoff, Henrik; Raudaschl-Sieber, Gabriele; Kirchhain, Holger; Sedlmeier, Christian; van Wüllen, Leo; Gasteiger, Hubert A.; Fässler, Thomas F. (2020-08-25). "Modifying the Properties of Fast Lithium-Ion Conductors—The Lithium Phosphidotetrelates Li 14 SiP 6 , Li 14 GeP 6 , and Li 14 SnP 6" . Chemistry of Materials. 32 (16): 6925–6934. doi:10.1021/acs.chemmater.0c02052. ISSN   0897-4756. S2CID   225445668.
  8. Eickhoff, H.; Klein, W.; Toffoletti, L.; Raudaschl-Sieber, G.; Fässler, T. F. (2022-05-25). "Planar Si 5 and Ge 5 Pentagons beside Isolated Phosphide Anions in Lithium Phosphide Tetrelides Li 10+x Si 5 P and Li 10+x Ge 5 P". Zeitschrift für anorganische und allgemeine Chemie. 648 (10). doi: 10.1002/zaac.202100376 . ISSN   0044-2313. S2CID   246183043.
  9. Feng, Kai; Yin, Wenlong; He, Ran; Lin, Zheshuai; Jin, Shifeng; Yao, Jiyong; Fu, Peizhen; Wu, Yicheng (2012). "NaGe 3 P 3 : a new ternary germanium phosphide featuring an unusual [Ge 3 P 7 ] ring" . Dalton Trans. 41 (2): 484–489. doi:10.1039/C1DT11345C. ISSN   1477-9226. PMID   22042509.
  10. 1 2 Eickhoff, Henrik; Hlukhyy, Viktor; Fässler, Thomas F. (2020-11-30). "Na 2 Ge 3 P 3 and Na 5 Ge 7 P 5 Comprising Heteroatomic Polyanions Mimicking the Structure of Fibrous Red Phosphorus". Zeitschrift für anorganische und allgemeine Chemie. 646 (22): 1834–1838. doi: 10.1002/zaac.202000316 . ISSN   0044-2313. S2CID   225006755.
  11. Botta, Manuel; Zeitz, Sabine; Klein, Wilhelm; Raudaschl-Sieber, Gabriele; Fässler, Thomas F. (2024-04-19). "Na 3 Ge 2 P 3 : A Zintl Phase Featuring [P 3 Ge–GeP 3 ] Dimers as Building Blocks". Inorganic Chemistry. 63 (43): 20108–20116. doi: 10.1021/acs.inorgchem.4c00287 . ISSN   0020-1669. PMC   11523322 .
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  14. Boyd, G. D.; Buehler, E.; Storz, F. G. (1971-04-01). "LINEAR AND NONLINEAR OPTICAL PROPERTIES OF ZnGeP2 AND CdSe" . Applied Physics Letters. 18 (7): 301–304. Bibcode:1971ApPhL..18..301B. doi:10.1063/1.1653673. ISSN   0003-6951.
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  16. Buehler, E.; Wernick, J. H.; Wiley, J. D. (August 1973). "The ZnP2-Ge system and growth of single crystals of ZnGeP2" . Journal of Electronic Materials. 2 (3): 445–454. Bibcode:1973JEMat...2..445B. doi:10.1007/BF02660148. ISSN   0361-5235. S2CID   94941316.
  17. Nowak, E.; Neumann, H.; Omar, M. S. (January 1988). "Heat capacity of Ag6Ge10p12 from 180 to 550 K" . Crystal Research and Technology. 23 (1): 103–106. Bibcode:1988CryRT..23..103N. doi:10.1002/crat.2170230114.
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  20. Masumoto, K.; Isomura, S.; Goto, W. (November 1966). "The preparation and properties of ZnSiAs2, ZnGeP2 and CdGeP2 semiconducting compounds" . Journal of Physics and Chemistry of Solids. 27 (11–12): 1939–1947. Bibcode:1966JPCS...27.1939M. doi:10.1016/0022-3697(66)90124-7.
  21. Eisenmann, Brigitte; Klein, Jürgen; Somer, Mehmet (January 1990). "Anions Isosteric with CO32− in Cs5SiP3, Cs5SiAs3, Cs5GeP3, and Cs5GeAs3" . Angewandte Chemie International Edition in English. 29 (1): 87–88. doi:10.1002/anie.199000871. ISSN   0570-0833.
  22. Chen, Jindong; Lin, Chensheng; Peng, Guang; Xu, Feng; Luo, Min; Yang, Shunda; Shi, Shuangshuang; Sun, Yingshuang; Yan, Tao; Li, Bingxuan; Ye, Ning (2019-12-24). "BaGe 2 Pn 2 (Pn = P, As): Two Congruent-Melting Non-chalcopyrite Pnictides as Mid- and Far-Infrared Nonlinear Optical Materials Exhibiting Large Second Harmonic Generation Effects" . Chemistry of Materials. 31 (24): 10170–10177. doi:10.1021/acs.chemmater.9b03863. ISSN   0897-4756. S2CID   212863749.