Thiogermanate Explained

Sulfidogermanates or thiogermanates are chemical compounds containing anions with sulfur atoms bound to germanium. They are in the class of chalcogenidotetrelates. Related compounds include thiosilicates, thiostannates, selenidogermanates, telluridogermanates and selenidostannates.

Coordination of sulfur around germanium is tetrahedral meaning there are four sulfur atoms symmetrically arranged. This basic structure can form ortho salts with GeS₄⁴⁻, oligomers, or polymeric structures.^[1] Similar structures are also formed with heavy group 13 and group 14 elements due to their relatively stronger bonds with sulfur. Light elements from these groups have lower affinity for sulfur, so there are fewer compounds like this for boron, aluminium, carbon, and silicon.^[1] Other heavy group 12 and 15 elements also form chalcogenidometallates which may have other kinds of coordination. Selenium forms similar compounds to sulfur in this family.^[1]

Where sulfur is deficient, an anion is not formed, and instead cation-like covalent compounds can exist with halogens, such as Ge₄S₆Br₄,^[2] or Ge₄S₆I₄.^[3]

Production

The solvochemical method of production involves dissolving germanium oxide, sulfur and other salts in a heated solvent under pressure. The solvents can include simple alcohols, amines or N,N-dimethyl formamide. The containers can be glass tubes, quartz tubes, or teflon lined stainless steel.^[1]

List

formula	name	system	space group	cell Å	volume	density	comments	ref
H4Ge4S10	thiogermanic acid	triclinic	P	a = 8.621, b = 9.899, c = 10.009, α = 85.963°, β = 64.714°, γ = 89.501°, Z = 2				^[4] ^[5]
H2Ge4S9	thiogermanic acid
Li2GeS3		hexagonal	P61	a = 6.79364 c = 17.9072				^[6]
[CH<sub>3</sub>NH<sub>3</sub>]4Ge2S6	tetrakis(methylammonium) bis(μ-sulfido)-tetrakis(sulfido)-di-germanium	triclinic	P	a 7.3336 b 7.3760 c 10.0007, α 108.598° β 111.332° γ 90.297°				^[7]
[CH<sub>3</sub>CH<sub>2</sub>NH<sub>3</sub>]4Ge2S6•CH3CH2NH2	tetrakis(ethylammonium) bis(μ-sulfido)-tetrakis(sulfido)-di-germanium ethylamine	orthorhombic	Pnma	a 7.8501 b 18.3444 c 17.4386
[CH<sub>3</sub>CH<sub>2</sub>NH<sub>3</sub>]3[CH<sub>3</sub>NH<sub>3</sub>]Ge4S10	tris(diethylammonium) methylammonium hexakis(μ-sulfido)-tris(sulfido)-tetra-germanium		Pa3	a 17.9402 c 17.9402
(NH4)2[NH<sub>2</sub>(CH<sub>3</sub>)<sub>2</sub>]2Ge2S6		monoclinic	P21/c	a = 6.965, b = 15.7195, c = 7.2045, β = 92.765°			band gap 3.50 eV	^[8]
(NH3NH2)2[(R<sup>N</sup>Ge)<sub>2</sub>(μ-S)<sub>2</sub>S<sub>2</sub>]								^[9]
[(R<sup>1</sup>Ge)<sub>4</sub>(μ-S)<sub>6</sub>]	R^1 = CMe2CH2COMe							^[10]
(trenH2)2[Ge<small><sub>2</sub></small>S<small><sub>6</sub></small>]	tren = tris(2-aminoethyl)amine	monoclinic	C2/c	a=25.264 b=7.313 c=16.584 β=122.616 Z=4	2581	1.632	colourless	^[11]
(enH)4Ge2S6	en = ethylenediamine	triclinic	P	a 7.859 b 9.514 c 9.727, α 64.21° β 66.80° γ 84.92°				^[12]
Na4Ge2S6 · 14H2O		triclinic	P	a = 9.978, b = 7.202, c = 9.601, α = 108.41 β = 92.39, γ = 91.69° Z = 1				^[13]
Na6Ge2S7								^[14]
Li4MgGe2S7		monoclinic	Cc	a=16.872 b=6.771 c=10.156 β=95.169°			SHG 0.7 ×AGS	^[15]
Na(AlS2)(GeS2)4		monoclinic	P21/n	a = 6.803, b = 38.207, c = 6.947, β = 119.17°				^[16]
Li10GeP2S12		tetragonal					lithium ion conductor	^[17]
K6Ge2S7
[VO(dien)]2GeS4		orthorhombic	Pna21	a =19.831, b = 8.0814, c = 12.0889, Z = 4	1937.4			^[18]
Ge2S6	en = ethylenediamine	monoclinic	P21/n	a=8.352 b=12.682 c=11.339  β=94.75 Z=2	1196.9	1.931	black	^[19]
[VO(dap)<small><sub>2</sub></small>]2Ge2S6·dap	dap = 1,2-diaminopropane	hexagonal	Rc ?	a=38.284 c=11.170 Z=18	14178	1.619	purple; hexagonal nanotubes
Li4MnGe2S7		monoclinic	Cc	a=16.833 b=6.709 c=10.121 β=94.76° Z=4	1139.1	2.637	light pink	^[20]
·3H2O	bipy = bipyridine	triclinic	P	a=10.6511 b=13.0443 c=22.995, α=79.539 β=77.653° γ=79.737° Z=2	3036.6	1.570		^[21]
2(μ-Ge2Se6)		tetragonal	I41/a					^[22]
Mn2(en)4Ge2S6	en=ethylenediamine							^[23]
[Mn(en)<sub>3</sub>]2Ge2S6		monoclinic	C2/c	a 15.115 b 10.530 c 22.897, 118.777°
Mn2(dap)4Ge2S6	dap = 1,2-diaminopropane
H2dienMnGeS4	dien = diethylenetriamine
[(dien)<sub>2</sub>Mn]Ge2S4	dien=diethylenetriamine	orthorhombic	P212121	a=9.113, b=12.475, c=17.077, Z=4	1941		1D [Ge<sub>2</sub>S<sub>4</sub>]^2− chains	^[24]
Mn3Ge2S7(NH3)4		orthorhombic	Pbcn	a=9.107 b=13.923 c=12.750 Z=4	1616.6	2.476	green	^[25]
[Mn<sup>II</sup>(tren)]2(μ2-Ge2S6)	tren = N,N,N-tris(2-aminoethyl)amine	triclinic	P	a 7.631 b 8.039 c 11.957, α 98.952° β 101.263° γ 109.696°				^[26]
[Mn<sup>II</sup>(tepa)]2(μ2-Ge2S6)	tepa= tetraethylenepentaamine	orthorhombic	I 41/a	a =25.770 b =25.770 c =9.812
[Fe(2,2′-bipy)<sub>3</sub>]2[Ge<sub>4</sub>S<sub>10</sub>]·10H2O		monoclinic	P21/c	a=23.8411 b=13.6462 c=22.9029 β=93.400° Z=4	7438.1	1.643
2(μ-Ge2Se6)		tetragonal	I41/a
K2FeGe3S8		triclinic	P	a = 7.016, b= 7.770, c = 14.342, α = 93.80°, β = 92.65°, γ = 114.04°				^[27]
K2CoGe3S8		monoclinic	P21	a = 7.1089, b = 11.8823, c = 16.759, β = 96.604°
[{Co(tepa)}<sub>2</sub>(μ-Ge<sub>2</sub>S<sub>6</sub>)]	tepa= tetraethylenepentaamine	tetragonal	I41/a
[dienH<small><sub>2</sub></small>][Co(dien)<small><sub>2</sub></small>][Ge<small><sub>2</sub></small>S<small><sub>6</sub></small>]	dien = diethylenetriamine	triclinic	P	a 11.3224 b 14.6492 c 18.3710, α 71.000° β 78.352° γ 73.441° Z=4	2741.5	1.715	yellow	^[28]
[dienH<small><sub>2</sub></small>][Co(dien)<small><sub>2</sub></small>][Ge<small><sub>2</sub></small>S<small><sub>6</sub></small>]		triclinic	P	a 11.3224 b 14.6492 c 18.3710, α 71.000° β 78.352° γ 73.441° Z=1	679.62	1.730	yellow
[dienH<small><sub>2</sub></small>][Co(dien)<small><sub>2</sub></small>][Ge<small><sub>2</sub></small>S<small><sub>6</sub></small>]		orthorhombic	Pbca	a=15.2110 b=16.7025 c=21.8821 Z=8	5559.4	1.692	yellow
[dienH<small><sub>2</sub></small>][Co(dien)<small><sub>2</sub></small>][Ge<small><sub>2</sub></small>S<small><sub>6</sub></small>]		orthorhombic	Pca21	a=a=14.7043 b=9.0099 c=21.4540 Z=4	2842.3	1.655	yellow
[Ni(cyclam)]3[Ni(cyclam)(H<sub>2</sub>O)<sub>2</sub>][Ge<sub>4</sub>S<sub>10</sub>]2·21H2O	cyclam = 1,4,8,11-tetraazacyclotetradecane	monoclinic	Cc	a=35.915 b=10.047 c=30.607 β =115.32 Z=4	9983	1.778
[Ni(en)<sub>3</sub>]2Ge2S6	en=ethylenediamine	orthorhombic	Pbca	a 15.56 b 11.226 c 18.07
[Ni(dien)<sub>2</sub>]3[Ge<sub>3</sub>Sb<sub>8</sub>S<sub>21</sub>]·0.5H2O	dien = diethylenetriamine							^[29]
[Ni(trien)<sub>2</sub>]2Ge4S10	bis(bis(triethylenetetramine)-nickel) hexakis(μ2-sulfido)-tetrasulfido-tetra-germanium	monoclinic	C2/c	a =21.618 b =10.957 c =22.719, β=111.224°				^[30]
[{Ni(tepa)}<sub>2</sub>(''μ''-Ge<sub>2</sub>S<sub>6</sub>)]	tetrakis(μ2-sulfido)-disulfido-bis(tetraethylenepentamine)-di-germanium-di-nickel	orthorhombic	Pbca	a =15.151 b =13.083 c =15.255
[Ni<sup>II</sup>(dien)<sub>2</sub>]2(Ge2S6)	dien = diethylenetriamine	monoclinic	P 21/n	a 10.093 b 14.219 c 11.703, β 91.631°
[Ni<sup>II</sup>(dien)<sub>2</sub>](H2pipe)(Ge2S6)	pipe = piperazine	triclinic	P	a 6.980 b 8.530 c 11.527, α 93.03° β 106.29° γ 101.95°
[Ni<sup>II</sup>(tepa)]2(μ2-Ge2S6)	tepa = tetraethylenepentamine	orthorhombic	Pbca	a =15.147 b =13.0552 c =15.238
[(CH<sub>3</sub>CH<sub>2</sub>)<sub>4</sub>N]3CuGe4S10	catena-[hexakis(tetraethylammonium) hexadecakis(μ-sulfido)-tetrakis(sulfido)-octa-germanium-di-copper]	monoclinic	P 21/n	a 15.0956 b 14.2127 c =19.5889, β 91.131°
[H<sub>4</sub>teta]5[Cu<sub>40</sub>Ge<sub>15</sub>S<sub>60</sub>]·2.5(teta)								^[31]
Cu(AlS2)(GeS2)4		monoclinic	P21/n	a 6.796 b 37.628 c 6.8797, β 119.52°
Cu4MnGe2S7		monoclinic	Cc	a=16.7443 b=6.47893 c=9.8060 β=93.188°
Cu4FeGe2S7		monoclinic	C2	a=11.7405 b=5.3589 c=8.3420 β=98.661°
Cu4CoGe2S7		monoclinic	C2	a=11.7280 b=5.3399 c=8.3313 β=98.668°
Cu4NiGe2S7		monoclinic	C2	a=11.703 b=5.333 c=8.311 β=98.37°
Sr2CoGe2OS6		tetrahedral	P21m	a=9.4056 c=6.1741 Z=2	546.19	3.574	dark green; oxysulfide	^[32]
Y3LiGeS7								^[33]
[Y<small><sub>2</sub></small>(tepa)<small><sub>2</sub></small>(μ-OH)<small><sub>2</sub></small>(μ-Ge<small><sub>2</sub></small>S<small><sub>6</sub></small>)](tepa)0.5·H2O		monoclinic	C2/c	a=19.638 b=14.415 c=16.910 β=122.47 Z=4	4038.6	1.863	colourless
KYGeS4								^[34]
[{R<sup>N</sup>Ge(μ-S)<sub>3</sub>}<sub>4</sub>Pd<sub>6</sub>]·MeOH	R^N = CMe2CH2CMeNNH2
Ag10Ge3S11		monoclinic	Cc	a = 2.6244 b = 0.65020 c = 2.5083 β = 109.910°				^[35]
[(CH<sub>3</sub>CH<sub>2</sub>)<sub>4</sub>N]3AgGe4S10	catena-[hexakis(tetraethylammonium) hexadecakis(μ-sulfido)-tetrakis(sulfido)-di-silver-octa-germanium]	monoclinic	P 21/n	a 15.1898 b 14.3043 c 19.5059, β 91.056°
Ag(AlS2)(GeS2)4		monoclinic	P21/n	a 6.799 b 38.4169 c 6.813 β 119.65°
Li4CdGe2S7		monoclinic	Cc	a=17.4432 b=6.9353 c=10.3271 β=93.9042°
Na4CdGe2S7		monoclinic	P21/c	a=7.0813 b=11.9007 c=15.5759 β=90.791°
Y3Cd0.5GeS7
Ag4SnGe2S7		monoclinic	Cc	a=11.3398 b=6.9706 c=15.4885 β=91.213°			yellow; ∞[SnGe<sub>2</sub>S<sub>8</sub>]^6– chains
Na9Sb(Ge2S6)2		monoclinic	C2/m	a=7.5857 b=11.574 c=6.817 β=106.587 Z=1	573.7	2.905	yellow	^[36]
[Ge(en)<sub>3</sub>][GeSb<sub>2</sub>S<sub>6</sub>]		orthorhombic	Pbca
[(Me)<sub>2</sub>NH<sub>2</sub>]6[Ge<sub>2</sub>Sb<sub>2</sub>S<sub>7</sub>][Ge<sub>4</sub>S<sub>10</sub>]		triclinic	P				microporous, can exchange dimethyl ammonium for alkalis	^[37]
[dabcoH]2[Ge<sub>2</sub>Sb<sub>3</sub>S<sub>10</sub>]	dabco = 1,4-diazabicyclo[2.2.2]octane
DMAH[dabcoH]2[Ge<sub>2</sub>Sb<sub>3</sub>S<sub>10</sub>]	dabco = 1,4-diazabicyclo[2.2.2]octane	monoclinic	C2
[DMAH]2GeSb3S6			P41212
[AEPH<sub>2</sub>][GeSb<sub>2</sub>S<sub>6</sub>]·CH3OH	AEP = N-(2-aminoethyl)piperazine	orthorhombic	Pbca	a=6.7183 b=18.3065 c=31.5007 Z=8	3874.2	2.303	yellow	^[38]
[CH<sub>3</sub>NH<sub>3</sub>]20Ge10Sb28S72·7H2O		monoclinic	C2/c	a =29.2964 b=29.3261 c=41.601 β=100.084°				^[39]
[(CH<sub>3</sub>CH<sub>2</sub>CH<sub>2</sub>)<sub>2</sub>NH<sub>2</sub>]3Ge3Sb5S15·0.5(C2H5OH)		triclinic	P	a=9.7628 b=15.7590 c=17.0313, α=79.868° β=75.010° γ=81.094°
[Mn(en)<sub>3</sub>][GeSb<sub>2</sub>S<sub>6</sub>]	dien = diethylenetriamine	orthorhombic	Pbca	a=13.374 b=17.607 c=18.562 Z=8	4370.8	2.26	yellow	^[40]
[Co(en)<sub>3</sub>][GeSb<sub>2</sub>S<sub>6</sub>]		orthorhombic	Pbca
[Co(dien)<sub>2</sub>]2[GeSb<sub>4</sub>S<sub>10</sub>]	dien = diethylenetriamine	orthorhombic	Pbca	a=14.684 b=17.133 c=33.478 Z=8	8422	2.205	yellow
[Ni(en)<sub>3</sub>][GeSb<sub>2</sub>S<sub>6</sub>]		orthorhombic	Pbca
[Ni(dien)<sub>2</sub>]3[Ge<sub>3</sub>Sb<sub>8</sub>S<sub>21</sub>]·0.5H2O		monoclinic	C2/m	a =17.604 b =30.660 c =15.348 β =114.69°
La(dien)2(μ–η^1,η^2-GeS3(SH))		monoclinic	C2/c	a=27.837 b=16.993 c=8.318 β =103.96 Z=8	3818.7	1.903	red	^[41]
KLaGeS4		monoclinic	P21	a=6.6645 b=6.7079 c=8.7248 β=107.519° Z=2	371.95		SHG 1.2×AgGaS2; band gap 3.34 eV; birefringence 0.098 @ 1064 nm
Nd(dien)2(μ–η^1,η^2-GeS3(SH))		monoclinic	C2/c	a=27.694 b=16.845 c=8.287 β =103.791 Z=8	3754.4	1.955	red
[Pr(dien)<small><sub>3</sub></small>]2[Ge<small><sub>2</sub></small>S<small><sub>6</sub></small>]Cl2	dien = diethylenetriamine	monoclinic	P21/n	a=11.637 b=14.143 c=15.120 β=98.149° Z=4	2463	1.765	green	^[42]
[Sm(dien)<small><sub>3</sub></small>]2[Ge<small><sub>2</sub></small>S<small><sub>6</sub></small>]Cl2	dien = diethylenetriamine	monoclinic	P21/n	11.532 b=14.423 c=14.573 β=97.105° Z=4	2405	1.834	light yellow
Sm3Zn0.5GeS7
Eu3Ge3S9				a=8.468 b=11.76 c=8.389 α=90.49° β=104.56° γ=69.53° Z=2		4.22 meas		^[43]
[Eu(dien)<small><sub>3</sub></small>]2[Ge<small><sub>2</sub></small>S<small><sub>6</sub></small>]Cl2	dien = diethylenetriamine	monoclinic	P21/n	a=11.567 b=14.633 c=14.465 β=96.434 Z=4	2432.9	1.818	yellow
Gd3Cd0.5GeS7
[Gd(dien)<small><sub>3</sub></small>]2[Ge<small><sub>2</sub></small>S<small><sub>6</sub></small>]Cl2	dien = diethylenetriamine	monoclinic	P21/n	11.548 b=14.677 c=14.427 β=96.332° Z=4	2430.4	1.834	colourless
[Dy(dien)<small><sub>3</sub></small>]2[Ge<small><sub>2</sub></small>S<small><sub>6</sub></small>]Cl2	dien = diethylenetriamine	monoclinic	P21/n	a=11.503 b=14.645 c=14.340 β=96.178° Z=4	2401.8	1.870	light yellow
[Ho(trien)(en)GeS<small><sub>3</sub></small>(SH)]	trien = triethylenetetramine
Er2(tepa)2(μ-OH)2(μ-Ge2S6)]n·nH2O	tepa = tetraethylenepentamine							^[44]
[Er<small><sub>2</sub></small>(dien)<small><sub>4</sub></small>(μ-OH)<small><sub>2</sub></small>][Ge<small><sub>2</sub></small>S<small><sub>6</sub></small>]	dien = diethylenetriamine	monoclinic	P21/n	11.710 b=11.318 c=13.548 β=97.635° Z=4	1779.6	2.088	red
Tm2(tepa)2(μ-OH)2(μ-Ge2S6)]n·nH2O	tepa = tetraethylenepentamine
Li4HgGe2S7		monoclinic	Cc	a=16.876 b=6.7764 c=10.161 β=93.360°
Ag4HgGe2S7		monoclinic	Cc	a=17.4546 b=6.8093 c=10.5342 β=93.3980°
[(Me)<sub>2</sub>NH<sub>2</sub>][BiGeS<sub>4</sub>]		monoclinic	P21	a=6.7290 b c=10.6748 β=105.789 Z=2	479.72	3.156	red	^[45]

Notes and References

1. Wang . Kai-Yao . Feng . Mei-Ling . Huang . Xiao-Ying . Li . Jing . Organically directed heterometallic chalcogenidometalates containing group 12(II)/13(III)/14(IV) metal ions and antimony(III) . Coordination Chemistry Reviews . September 2016 . 322 . 41–68 . 10.1016/j.ccr.2016.04.021.
2. Pohl . Siegfried . Ge₄S₆Br₄—The First Sulfide Halide of Germanium . Angewandte Chemie International Edition in English . March 1976 . 15 . 3 . 162 . 10.1002/anie.197601621.
3. Pohl . Siegfried . Seyer . Ulrich . Krebs . Bernt . Sulfidhalogenide des Germaniums: Darstellung und Strukturen von Ge 4 S 6 Br 4 und Ge 4 S 6 I 4 / Thiohalides of Germanium: Preparation and Structures of Ge 4 SeBr 4 and Ge 4 S 6 I 4 . Zeitschrift für Naturforschung B . 1 November 1981 . 36 . 11 . 1432–1443 . 10.1515/znb-1981-1116. 93779728 . free .
4. Poling. Steven A.. Nelson. Carly R.. Sutherland. Jacob T.. Martin. Steve W.. 2003-06-01. Synthesis and Characterization of the Thiogermanic Acids H 4 Ge 4 S 10 and H 2 Ge 4 S 9. The Journal of Physical Chemistry B. en. 107. 23. 5413–5418. 10.1021/jp027313w. 1520-6106.
5. Poling. Steven A.. Nelson. Carly R.. Sutherland. Jacob T.. Martin. Steve W.. 2003-11-01. Crystal Structure of Thiogermanic Acid H 4 Ge 4 S 10. Inorganic Chemistry. en. 42. 23. 7372–7374. 10.1021/ic034659s. 14606829. 0020-1669.
6. Roh . Jihun . Do . Namgyu . Manjón-Sanz . Alicia . Hong . Seung-Tae . 2023-10-02 . Li 2 GeS 3 : Lithium Ionic Conductor with an Unprecedented Structural Type . Inorganic Chemistry . en . 62 . 39 . 15856–15863 . 10.1021/acs.inorgchem.3c01431 . 0020-1669.
7. Wang. Kai-Yao. Zhang. Shu. Liu. Hua-Wei. Cheng. Lin. Wang. Cheng. 2019-10-07. Stepwise Conversion from GeO 2 to [MGe 4 S 10 ] n 3 n – (M = Cu, Ag) Polymer via Isolatable [Ge 2 S 6 ] 4– and [Ge 4 S 10 ] 4– Anions by Virtue of Templating Technique]. Inorganic Chemistry. en. 58. 19. 12832–12842. 10.1021/acs.inorgchem.9b01779. 31490672. 201869666. 0020-1669.
8. Zhang. Jian-Han. Su. Zhi-Zhong. Luo. Ju-Xiang. Zhao. Yi. Wang. Hong-Gang. Ying. Shao-Ming. May 2020. Synthesis, structure, and characterization of a mixed amines thiogermanate [NH4]2[NH2(CH3)2]2Ge2S6]. Polyhedron. en. 182. 114486. 10.1016/j.poly.2020.114486. 216378118.
9. Halvagar. Mohammad Reza. Hassanzadeh Fard. Zohreh. Xiong. Lin. Dehnen. Stefanie. 2009-08-03. Facile Access to the Hydrazone Functionalized PdGeS Cluster [{R N Ge(μ-S) 3 } 4 Pd 6 ] from the Thiogermanate Anion [{R N Ge} 2 (μ-S) 2 S 2 ] 2−]. Inorganic Chemistry. en. 48. 15. 7373–7377. 10.1021/ic900853e. 19586024. 0020-1669.
10. Eußner. Jens P.. Dehnen. Stefanie. September 2012. Formation of Thiosemicarbazone-Functionalized Complexes with (GeS 2) 2 and (SnS 2) 2 Units. Zeitschrift für anorganische und allgemeine Chemie. de. 638. 11. 1827–1832. 10.1002/zaac.201200292. free.
11. Liu. Xing. Hu. Feilong. Zhou. Jian. An. Litao. Liang. Dawen. Lin. Jianwu. 2012. Solvothermal synthesis, crystal structures and properties of three new thiogermanates: the only example of the thiogermanate anion [Ge2S6]4− as a bridging ligand to a lanthanide complex ion]. CrystEngComm. en. 14. 10. 3464. 10.1039/c2ce25082a. 1466-8033.
12. Jia . Ding-Xian . Dai . Jie . Zhu . Qin-Yu . Cao . Li-Hui . Lin . Hai-Hong . March 2005 . Solvothermal synthesis of three new dimeric thiogermanates (enH)4Ge2S6, [Mn(en)3]2Ge2S6 and [Ni(en)3]2Ge2S6 from germanium dioxide and sulfur powder ]. Journal of Solid State Chemistry . en . 178 . 3 . 874–881 . 10.1016/j.jssc.2004.07.045. 2005JSSCh.178..874J .
13. Krebs. B.. Pohl. S.. Schiwy. W.. November 1972. Darstellung und Struktur von Na4Ge2S6 . 14H2O und Na4Sn2S6 . 14H2O. Zeitschrift für anorganische und allgemeine Chemie. de. 393. 3. 241–252. 10.1002/zaac.19723930307. 0044-2313.
14. Willard. Hobart H.. Zuehlke. C. W.. October 1943. The Preparation and Properties of Potassium Thiogermanate and Thiogermanic Acid 1. Journal of the American Chemical Society. en. 65. 10. 1887–1889. 10.1021/ja01250a026. 0002-7863.
15. Wang . Peng . Abudoureheman . Maierhaba . Zhang . Kewang . Zheng . Juanjuan . Chen . Zhaohui . Wu . Qi . 2022-10-03 . Ag 4 SnGe 2 S 7 : A Noncentrosymmetric Chalcogenide in I 4 –II–IV 2 –VI 7 System with Non-Diamond-Like Structure Featuring 1D ∞ [SnGe 2 S 8 ] 6– Infinite Chain ]. Inorganic Chemistry . en . 61 . 39 . 15303–15309 . 10.1021/acs.inorgchem.2c01828 . 36126330 . 252405280 . 0020-1669.
16. Alahmari. Fatimah. Davaasuren. Bambar. Emwas. Abdul-Hamid. Rothenberger. Alexander. 2018-04-02. Thioaluminogermanate M (AlS 2)(GeS 2) 4 (M = Na, Ag, Cu): Synthesis, Crystal Structures, Characterization, Ion-Exchange and Solid-State 27 Al and 23 Na NMR Spectroscopy. Inorganic Chemistry. en. 57. 7. 3713–3719. 10.1021/acs.inorgchem.7b02980. 29537828. 10754/627415. 0020-1669. free.
17. Xu. Miao. Song. Subin. Daikuhara. Shugo. Matsui. Naoki. Hori. Satoshi. Suzuki. Kota. Hirayama. Masaaki. Shiotani. Shinya. Nakanishi. Shinji. Yonemura. Masao. Saito. Takashi. 2022-01-10. Li 10 GeP 2 S 12 -Type Structured Solid Solution Phases in the Li 9+δ P 3+δ′ S 12– k O k System: Controlling Crystallinity by Synthesis to Improve the Air Stability. Inorganic Chemistry. en. 61. 1. 52–61. 10.1021/acs.inorgchem.1c01748. 34914367. 245270702. 0020-1669. free.
18. Wang. Jing. Näther. Christian. Djamil. John. Bensch. Wolfgang. August 2012. [VO(dien)]2GeS4: Solvothermal Synthesis and Crystal Structure with an Ortho-Thiogermanate as Tetradentate Ligand]. Zeitschrift für anorganische und allgemeine Chemie. en. 638. 10. 1452–1456. 10.1002/zaac.201200174.
19. Qian. Li-Wen. Zhao. Xiao-Wei. Su. Hu-Chao. Bian. Guo-Qing. Zhu. Qin-Yu. Dai. Jie. 2016. Supramolecular hexagonal nano tubes assembled by vanadium diamine complexes with thiogermanates. RSC Advances. en. 6. 20. 16268–16273. 10.1039/C5RA27088J. 2016RSCAd...616268Q. 2046-2069.
20. Kaib . Thomas . Haddadpour . Sima . Andersen . Hanne Flåten . Mayrhofer . Leonhard . Järvi . Tommi T. . Moseler . Michael . Möller . Kai-Christian . Dehnen . Stefanie . 2013-12-10 . Quaternary Diamond-Like Chalcogenidometalate Networks as Efficient Anode Material in Lithium-Ion Batteries . Advanced Functional Materials . en . 23 . 46 . 5693–5699 . 10.1002/adfm.201301025 . 93236286.
21. Danker. Felix. Näther. Christian. Pielnhofer. Florian. Bensch. Wolfgang. 2017-10-10. Room‐Temperature Synthesis of Three Compounds Featuring the [Ge 4 S 10 ] 4– Anion from a Water‐Soluble Thiogermanate Precursor]. European Journal of Inorganic Chemistry. en. 2017. 37. 4317–4323. 10.1002/ejic.201700795. 1434-1948.
22. Chen. Jiang-Fang. Jin. Qin-Yan. Pan. Ying-Li. Zhang. Yong. Jia. Ding-Xian. January 2010. Solvothermal Syntheses and Characterization of New Transition Metal Chalcogenidogermanates [{Co(tepa)} 2 (μ-Ge 2 S 6)] and [{M(tepa)} 2 (μ-Ge 2 Se 6)] (M = Mn, Fe) (tepa = Tetraethylenepentamine)]. Zeitschrift für anorganische und allgemeine Chemie. en. 636. 1. 230–235. 10.1002/zaac.200900141.
23. Luo. Hai-Ying. Zhou. Jian. Cao. Shumei. 2019. A series of new hybrid chalcogenogermanates: the rare examples of chalcogenogermanates combined with trivalent vanadium complexes. Dalton Transactions. en. 48. 29. 10907–10914. 10.1039/C9DT02077B. 31282904. 195828996. 1477-9226.
24. Yue. Cheng-Yang. Yuan. Zhuang-Dong. Zhang. Lu-Ge. Wang. Ya-Bai. Liu. Guo-Dong. Gong. Liao-Kuo. Lei. Xiao-Wu. October 2013. Synthesis, crystal structure and properties of [(dien)2Mn]Ge2S4 with mixed-valent Ge centers]. Journal of Solid State Chemistry. en. 206. 129–133. 10.1016/j.jssc.2013.07.036. 2013JSSCh.206..129Y.
25. Zhang. Guodong. Li. Peizhou. Ding. Junfeng. Liu. Yi. Xiong. Wei-Wei. Nie. Lina. Wu. Tom. Zhao. Yanli. Tok. Alfred Iing Yoong. Zhang. Qichun. 2014-10-06. Surfactant-Thermal Syntheses, Structures, and Magnetic Properties of Mn–Ge–Sulfides/Selenides. Inorganic Chemistry. en. 53. 19. 10248–10256. 10.1021/ic501282d. 25208101. 0020-1669.
26. Liu. Guang-Ning. Guo. Guo-Cong. Wang. Ming-Sheng. Cai. Li-Zhen. Huang. Jin-Shun. November 2010. Five dimeric thiogermanates with transition metal complexes of multidentate chelating amines: Syntheses, structures, magnetism and photoluminescence. Journal of Molecular Structure. en. 983. 1–3. 104–111. 10.1016/j.molstruc.2010.08.039. 2010JMoSt.983..104L.
27. Ji. Bingheng. Pandey. Krishna. Harmer. Colin P.. Wang. Fei. Wu. Kui. Hu. Jin. Wang. Jian. 29 June 2021. Centrosymmetric or Noncentrosymmetric? Transition Metals Talking in K 2 TGe 3 S 8 (T = Co, Fe). Inorganic Chemistry. 60. 14. 10603–10613. 10.1021/acs.inorgchem.1c01149. 34185995. 1810574 . 235685892.
28. Lichte. Jessica. Näther. Christian. Bensch. Wolfgang. 2014-05-02. Polymorphism and tautomerism in [dienH 2 ][Co(dien) 2 ][Ge 2 S 6 ] leading to different hydrogen bonded networks]. CrystEngComm. en. 16. 25. 5551–5559. 10.1039/C4CE00312H. 94547016 . 1466-8033. free.
29. Zhou. Jian. Liu. Xing. Liang. Guoming. Liang. Weijiang. Hu. Feilong. Zhu. Ligang. January 2013. [Ni(dien)2]3[Ge3Sb8S21]·0.5H2O: A new 2-D layered thiogermanate–thioantimonate with metal complexes as template ions]. Inorganic Chemistry Communications. en. 27. 92–96. 10.1016/j.inoche.2012.10.015.
30. Liang. Jing-Jing. Zhao. Jing. Tang. Wei-Wei. Zhang. Yong. Jia. Ding-Xian. June 2011. Ethylene polyamine influence on the transition metal thiogermanates: Solvothermal syntheses and characterizations of [Ni(trien)2]2Ge4S10 and [{Ni(tepa)}2(μ-Ge2S6)]]. Inorganic Chemistry Communications. en. 14. 6. 1023–1026. 10.1016/j.inoche.2011.03.062.
31. Tang. Shimei. Zhou. Jian. Liu. Xing. Xiao. Hong-Ping. June 2018. A new 3-D cuprous thiogermanate with rare 3-D [Cu-S-Cu]n network]. Materials Today Communications. en. 15. 88–93. 10.1016/j.mtcomm.2018.02.035. 103265774.
32. Zhang . Nan . Xu . Qian-Ting . Shi . Zhi-Hui . Yang . Mei . Guo . Sheng-Ping . 2022-10-31 . Characterizations and Nonlinear-Optical Properties of Pentanary Transition-Metal Oxysulfide Sr 2 CoGe 2 OS 6 . Inorganic Chemistry . en . 61 . 43 . 17002–17006 . 10.1021/acs.inorgchem.2c03283 . 36265201 . 253044751 . 0020-1669.
33. Gao . Lihua . Wu . Xiaowen . Xu . Jingjing . Tian . Xinyu . Zhang . Bingbing . Wu . Kui . Rational combination of multiple structural groups on regulating nonlinear optical property in hexagonal Ln3MGeS7 polar crystals . Journal of Alloys and Compounds . December 2021 . 900 . 163535 . 10.1016/j.jallcom.2021.163535. 245626019 .
34. Liu . Yang . Li . Xiangming . Wu . Shuchang . Ma . Mengjie . Jiang . Xiaoming . Wu . Yuandong . Mei . Dajiang . 2024-06-03 . A Rare Earth Chalcogenide Nonlinear Optical Crystal KLaGeS 4 : Achieving Good Balance among Band Gap, Second Harmonic Generation Effect, and Birefringence . Inorganic Chemistry . en . 10.1021/acs.inorgchem.4c00842 . 0020-1669.
35. Fedorchuk . A.O. . Lakshminarayana . G. . Tokaychuk . Y.O. . Parasyuk . O.V. . November 2013 . The crystal structure of novel silver sulphogermanate Ag10Ge3S11 . Journal of Alloys and Compounds . en . 576 . 134–139 . 10.1016/j.jallcom.2013.04.110.
36. Wu. Xiaowen. Hu. Yi. Pan. Hui. Su. Zhi. 2016. Na 9 Sb(Ge 2 Q 6) 2 (Q = S, Se): two new antimony(iii) quaternary chalcogenides with ethane-like [Ge 2 Q 6 ] 6− ligands]. RSC Advances. en. 6. 101. 99475–99481. 10.1039/C6RA22000B. 2046-2069.
37. Feng. Mei-Ling. Kong. De-Nian. Xie. Zai-Lai. Huang. Xiao-Ying. 2008-10-27. Three-Dimensional Chiral Microporous Germanium Antimony Sulfide with Ion-Exchange Properties. Angewandte Chemie International Edition. en. 47. 45. 8623–8626. 10.1002/anie.200803406. 18846520.
38. Feng. Mei-Ling. Hu. Chun-Li. Wang. Kai-Yao. Du. Cheng-Feng. Huang. Xiao-Ying. 2013. [AEPH2][GeSb2S6]·CH3OH: a thiogermanate–thioantimonate featuring an infinite ribbon-like structure with an unusual unit and exhibiting the ability of photocatalytic degradation of organic dye]. CrystEngComm. en. 15. 25. 5007. 10.1039/c3ce40143j. 1466-8033.
39. Zhang. Bo. Feng. Mei-Ling. Cui. Hong-Hua. Du. Cheng-Feng. Qi. Xing-Hui. Shen. Nan-Nan. Huang. Xiao-Ying. 2015-09-08. Syntheses, Crystal Structures, Ion-Exchange, and Photocatalytic Properties of Two Amine-Directed Ge–Sb–S Compounds. Inorganic Chemistry. en. 54. 17. 8474–8481. 10.1021/acs.inorgchem.5b01181. 26291119. 0020-1669.
40. Zhou. Jian. An. Litao. Liu. Xing. Huang. Lijun. Huang. Xijiao. 2011. Solvothermal synthesis and characterization of two 2-D layered germanium thioantimonates with transition-metal complexes. Dalton Transactions. en. 40. 43. 11419–11424. 10.1039/c1dt11280e. 21931916. 1477-9226.
41. Zhou . Jian . Li . Rong . Ling . Xing . Chen . Rong . Hu . Feilong . Zeng . Yanfang . 2013 . The first examples of thiogermanate anion [GeS 3 (SH)] 3− as a bridging ligand to a lanthanide complex ]. Dalton Trans. . en . 42 . 6 . 1961–1964 . 10.1039/C2DT32389C . 23165504 . 1477-9226.
42. Zhao. Rong-Qing. Zhou. Jian. Liu. Xing. Zhang. Li. Tang. Qiuling. Tan. Xiao-Feng. 2014-08-19. Solvothermal syntheses of lanthanide thiogermanates displaying three new structural moieties. RSC Advances. en. 4. 73. 38682. 10.1039/C4RA07812H. 2014RSCAd...438682Z. 2046-2069.
43. Bugli . G. . Carré . D. . Barnier . S. . 1978-11-01 . Structure cristalline du thiogermanate d'europium Eu 3 Ge 3 S 9 . Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry . 34 . 11 . 3186–3189 . 10.1107/S0567740878010456 . 0567-7408.
44. Tang. Shimei. Cao. Shumei. Zhou. Jian. July 2018. A Series of Lanthanide Chalcogenidogermanates Displaying Two Types of 1-D Polymeric Chains. Journal of Cluster Science. en. 29. 4. 777–783. 10.1007/s10876-018-1402-6. 103263516. 1040-7278.
45. Feng . Mei-Ling . Qi . Xing-Hui . Zhang . Bo . Huang . Xiao-Ying . 2014 . [(Me)2NH2][BiGeS4]

    the first organically directed bismuth thiogermanate with Rb+ ion exchange property ]

    . Dalton Transactions . en . 43 . 22 . 8184–8187 . 10.1039/c4dt00173g . 24781350 . 1477-9226.