Phosphidogermanate

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

formula	MW	crystal system	space group	unit cell Å	volume	density	form	properties	references
GeP		monoclinic	C2/m	a = 15.1948 b = 3.6337 c = 9.1941 β = 101.239°					^[3]
Li₂GeP₂	148.458	tetragonal	I4₁/acd	a = 12.3069 c = 19.0306 Z=32	2882.42	2.736	Ge₄P₁₀ supratetrahedra	red	^[4]
LiGe₃P₃	317.751	orthorhombic	Pbam	a = 9.8459 b = 15.7489 c = 3.5995 Z=4	558.15	3.780	GeP₄ and Ge(P₃Ge) tetrahedra in 5 and 6-membered rings making 2D slabs	black	^[4]
Li₈GeP₄	252		Pa3	a=11.80203 c=11.80203 Z=8	1643.88	2.037			^[5]^[6]
Li₈GeP₄	251.99	cubic	P43n	a=11.77294 Z=8	1635.98	2.046			^[5]^[6]
Li₁₄GeP₆		cubic	Fm3m	a=5.95667 Z=4		1.860		brown	^[2]^[7]
Li_10.1Ge₅P			Pnma	a=10.360 b=4.3072 c=24.267 Z=4	1082.8	2.86	Ge₅ rings	black; actually is a germanide phosphide	^[8]
NaGe₃P₃		orthorhombic	Pmc2₁	a=3.6276 b=8.407 c=10.332 Z=2	315.09	3.517	Ge₃P₇ ring	red; band gap 2.06 eV; semiconductor	^[9]
Na₂Ge₃P₃	356.72	monoclinic	C2/m	a = 17.639 b = 3.6176 c = 11.354 β = 92.74° Z=4	723.7	3.274		black	^[10]
Na₃Ge₂P₃	307.06	monoclinic	P2₁/c	a = 7.2894 b = 14.7725 c = 7.0528 β = 106.331° Z=4	728.8	2.798	Ge₂P₆ with shared P	black	^[11]
Na₅Ge₇P₅		monoclinic	C2/m	a = 16.168 b = 3.6776 c = 12.924 β = 91.30° Z=2	768.2	3.343		black	^[10]
Na₈GeP₄	380.4	cubic	Fd3m	a=13.4230 Z=8	2418.53	2.08943	same as Na₈SnSb₄	black; decomposes over 350°C to Na₁₀Ge₂P₆;band gap 1.9 eV	^[5]
Na₁₀Ge₂P₆		monoclinic	P2₁/n	a=13.176 b =7.36.4 c=8.042 β=90.26° Z=2	780.29	2.38		beige; moisture sensitive	^[12]
CuGe₂P₃									^[13]
ZnGeP₂			I42d	a=5.466 c=10.722				melt 1027°C	^[1]^[14]^[15]^[16]
Ag₆Ge₁₀P₁₂	1744.76	cubic	I43m	a=10.3111 Z=2	1096.3	5.286		air stable; silver grey; thermoelectric	^[17]^[18]^[19]
CdGeP₂			I42d	a=5.740 c=10.773					^[20]
Cs₅GeP₃		orthorhombic	Pnma	a=14.31 b=5.994 c=15.618 Z=4				metallic	^[21]
BaGe₂P₂	344.46	tetragonal	P4₂mc	a =7.6153 c =8.490 Z=4	492.3	4.647		light metallic grey; melt 861 °C	^[22]

References

^ ^a ^b 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.
^ ^a ^b 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.
^ 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.
^ ^a ^b 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.
^ ^a ^b ^c 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.
^ ^a ^b 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.
^ 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.
^ 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.
^ 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.
^ ^a ^b 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.
^ 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. doi:10.1021/acs.inorgchem.4c00287. ISSN 0020-1669.
^ Roesky, Herbert W.; Noltemeyer, Mathias; Sheldrick, George M. (1985-07-01). "Synthese und Struktur des Trifluoracetyldicyanomethanids". Zeitschrift für Naturforschung B. 40 (7): 883–890. doi:10.1515/znb-1985-0706. ISSN 1865-7117. S2CID 95632691.
^ Hailing, Tu; Saunders, G.A.; Omar, M.S.; Pamplin, B.R. (January 1984). "The elastic behaviour of the ternary zincblende structure semiconductor CuGe2P3". Journal of Physics and Chemistry of Solids. 45 (2): 163–172. Bibcode:1984JPCS...45..163H. doi:10.1016/0022-3697(84)90115-X.
^ 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.
^ Carnio, B. N.; Zhang, M.; Zawilski, K. T.; Schunemann, P. G.; Moutanabbir, O.; Elezzabi, A. Y. (19 May 2023). "Intra-pulse difference frequency generation in ZnGeP2 for high-frequency terahertz radiation generation". Scientific Reports. 13 (1): 8161. Bibcode:2023NatSR..13.8161C. doi:10.1038/s41598-023-35131-6. PMC 10199089. PMID 37208445.
^ 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.
^ 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.
^ Nuss, Jürgen; Wedig, Ulrich; Xie, Wenjie; Yordanov, Petar; Bruin, Jan; Hübner, Ralph; Weidenkaff, Anke; Takagi, Hidenori (2017-08-22). "Phosphide–Tetrahedrite Ag 6 Ge 10 P 12 : Thermoelectric Performance of a Long-Forgotten Silver-Cluster Compound". Chemistry of Materials. 29 (16): 6956–6965. doi:10.1021/acs.chemmater.7b02474. ISSN 0897-4756.
^ Namiki, H.; Kobayashi, M.; Nagata, K.; Saito, Y.; Tachibana, N.; Ota, Y. (June 2022). "Relationship between the density of states effective mass and carrier concentration of thermoelectric phosphide Ag6Ge10P12 with strong mechanical robustness". Materials Today Sustainability. 18: 100116. doi:10.1016/j.mtsust.2022.100116. S2CID 246977030.
^ 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.
^ 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.
^ 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.

[:1-1] 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.

[stran-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.

[:3-4] 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.

[:0-5] 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.

[:2-6] 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.

[:4-10] 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. doi:10.1021/acs.inorgchem.4c00287. ISSN 0020-1669.

[12] Roesky, Herbert W.; Noltemeyer, Mathias; Sheldrick, George M. (1985-07-01). "Synthese und Struktur des Trifluoracetyldicyanomethanids". Zeitschrift für Naturforschung B. 40 (7): 883–890. doi:10.1515/znb-1985-0706. ISSN 1865-7117. S2CID 95632691.

[13] Hailing, Tu; Saunders, G.A.; Omar, M.S.; Pamplin, B.R. (January 1984). "The elastic behaviour of the ternary zincblende structure semiconductor CuGe2P3". Journal of Physics and Chemistry of Solids. 45 (2): 163–172. Bibcode:1984JPCS...45..163H. doi:10.1016/0022-3697(84)90115-X.

[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.

[15] Carnio, B. N.; Zhang, M.; Zawilski, K. T.; Schunemann, P. G.; Moutanabbir, O.; Elezzabi, A. Y. (19 May 2023). "Intra-pulse difference frequency generation in ZnGeP2 for high-frequency terahertz radiation generation". Scientific Reports. 13 (1): 8161. Bibcode:2023NatSR..13.8161C. doi:10.1038/s41598-023-35131-6. PMC 10199089. PMID 37208445.

[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.

[18] Nuss, Jürgen; Wedig, Ulrich; Xie, Wenjie; Yordanov, Petar; Bruin, Jan; Hübner, Ralph; Weidenkaff, Anke; Takagi, Hidenori (2017-08-22). "Phosphide–Tetrahedrite Ag 6 Ge 10 P 12 : Thermoelectric Performance of a Long-Forgotten Silver-Cluster Compound". Chemistry of Materials. 29 (16): 6956–6965. doi:10.1021/acs.chemmater.7b02474. ISSN 0897-4756.

[19] Namiki, H.; Kobayashi, M.; Nagata, K.; Saito, Y.; Tachibana, N.; Ota, Y. (June 2022). "Relationship between the density of states effective mass and carrier concentration of thermoelectric phosphide Ag6Ge10P12 with strong mechanical robustness". Materials Today Sustainability. 18: 100116. doi:10.1016/j.mtsust.2022.100116. S2CID 246977030.

[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.

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Phosphidogermanate

List

References

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