Chemistry:Borosulfate

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The borosulfates are heteropoly anion compounds which have sulfate groups attached to boron atoms. Other possible terms are sulfatoborates or boron-sulfur oxides. The ratio of sulfate to borate reflects the degree of condensation. With [B(SO4)4]5- there is no condensation, each ion stands alone. In [B(SO4)3]3- the anions are linked into a chain, a chain of loops, or as [B2(SO4)6]6− in a cycle. Finally in [B(SO4)2]− the sulfate and borate tetrahedra are all linked into a two or three-dimensional network. These arrangements of oxygen around boron and sulfur can have forms resembling silicates. The first borosulfate to be discovered was K5[B(SO4)4] in 2012 by the research group of Henning Höppe,[1][2] although the compound class as such had been postulated already in 1962 by G. Schott and H. U. Kibbel.[3] Over 80 unique compounds are known as of 2024.

They are distinct from the borate sulfates which have separate, uncondensed sulfate and borate ions.

Related compounds include boroselenates, borotellurates,[4] and also boroantimonates, borogallates, borogermanates, borophosphates, boroselenites and borosilicates.[5]

Formation

Borosulfates are formed by heating boric oxide, oleum, or sulfuric acid, with metal carbonates. The degree of condensation is varied with the ratio of oleum to sulfuric acid. Pure oleum is more likely to yield compounds with disulfate groups.

Reactions

When heated to around 500 °C the borosulfates decompose by emitting SO3 vapour and form a metal sulfate and boric oxide.[6]

List

chem mw crystal system space group unit cell Å volume density comment references
boron sulfate B
2S
2O
9 		229.74 monoclinic C2 a=7.7600, b=4.1664, c=8.6134;

β=94.785°; Z=2

277.51 2.749 no cations; 3D mesh [7]
H[B(HSO
4)
4] 		monoclinic P21/c a=15.6974, b=11.436, c=8.5557;

β=90.334°; Z=8

superacid [8][9]
H
3O[B(SO
4)
2] 		P4/ncc a=9.1377, c=7.3423;

Z=4

[9]
H[B(SO
4)(S
2O
7)] 		monoclinic P21/c a=15.697, b=11.4362, c=8.5557;

β=90.334°

[4]
Li[B(SO
4)
2] 		Pc a=7.635, b=9.342, c=8.432;

β=92.55°

3D network, like tectosilicate [8][10]
Li[B(S
2O
7)
2] 		orthorhombic P212121 a=10.862, b=10.877, c=17.769 [8][10]
Li
5[B(SO
4)
4] 		orthorhombic P21/c a=8.0191, b=10.2111, c=15.0401 [4]
Be[B
2(SO
4)
4] 		monoclinic C2/c a=23.856, b=7.3507, c=12.3235;

β=98.724(2)°; Z=8

2136.1 2.58 colourless [11]
NH
4[B(SO
4)
2] 		P4/ncc a=9.1980, c=7.2458 decomposes at 320 °C (608 °F), proton conductor
NH
4[B(S
2O
7)
2] 		monoclinic Cc a=11.4403, b=14.9439, c=13.8693;

β=93.662°

[8][4]
(NH
4)
2B
4SO
10 		271.38 monoclinic C2 a=11.3685, b=6.5541, c=12.8328;

β=106.247°; Z=4

918.0 1.964 SHG 1.1 × KDP; min PM wavelength 252 nm; decompose 300 °C [12]
(NH
4)
3H
2[BOB(PO
4)
3] 		monoclinic P21/c a=7.7506, b=6.6685, c=24.355;

β=92.562°; Z=4

1257.5 2.000 white [13]
[NH
4]
3[B(SO
4)
3] 		343.12 orthorhombic Ibca a=7.2858, b=14.7048, c=22.7052;

Z=8

2433.2 1.928 decomposes 320 °C (608 °F) chains [14][2]
Na[B(SO
4)
2] 		monoclinic P2/c a=5.434, b=7.570, c=7.766;

β=99.74°

[4]
Na[B(S
2O
7)
2] 		monoclinic P21/c a=10.949, b=8.49, c=12.701;

β=110.227°; Z=4

[8][9]
Na
2B
6SO
13 		orthorhombic Pbca a=11.6569, b=9.4094, c=17.4833;

Z=8

1917.6 2.431 birefringence Δn = 0.07 @ 589.3 nm [15]
Na
5[B(SO
4)
4]-I
 		orthorhombic Pca21 a=10.730, b=13.891, c=18.197 [10]
Na
5[B(SO
4)
4]-II
 		orthorhombic P212121 a=8.624, b=9.275, c=16.671 [10]
Na
5[BOB(PO
4)
3] 		white [13]
α-Mg
4[B
2O(SO
4)
6] 		711.22 trigonal P3 a=8.0165 c=7.4858 Z=1 416.62 2.835 colourless [6]
β-Mg
4[B
2O(SO
4)
6] 		711.22 hexagonal P3 a = 13.9196, c = 7.4854, Z = 3 1253 2.821 colourless [6]
Mg[B
2(SO
4)
4] 		430.17 monoclinic C2/c a=17.443, b=5.3145, c=14.2906;

β=126.323°; Z=4

1067.3 2.677 phyllosilicate structure colourless decomposes 550 °C (1,022 °F) [6]
β-Mg[B
2(SO
4)
4] 		monoclinic P21/n a=7.9100, b=8.0815, c=9.0376;

β=111.37°; Z=2

269.01 2.667 colourless decomposes 550 °C (1,022 °F) [16]
Mg
3((H
2O)B(SO
4)
3)
2 		706.94 triclinic P1 a=7.9609, b=7.9671, c=9.2343;

α=64.959°, β=89.228°, γ=60.054°

444.96 2.638 200K [15]
Mg
3((H
2O)B(SO
4)
3)
2 		706.94 R3 a=7.9620, c=24.4231;

Z=3

1340.84 2.627 room temperature [15]
K[B(SO
4)
2] 		P4/ncc a=8.9739 c=7.4114 [4]
K[B(S
2O
7)
2] 		monoclinic Cc a=11.3368, b=14.66, c=13.6650;

β=94.235°; Z=8

[8][9]
K
2B
4SO
10 		313.50 monoclinic C2 a=11.2631, b=6.4339, c=12.649; 

β=105.707°; Z=4

882.4 2.360 colourless [17]
pentapotassium borosulfate K
5[B(SO
4)
4] 		P41 a=9.9023, c=16.1871 1687.2 2.471 first discovered [8][1]
K
3[B(SO
4)
3] 		orthorhombic Ibca a = 7.074, b = 14.266, c = 22.58 [8][10]
K
4[BS
4O
15(OH)] 		monoclinic I2/a a=14.524 b=7.3916 c=15.7857 β=115.50 [4]
K[B(SO3Cl)4] triclinic P1 a=10.513 b=10.838 c=10.965 α=99.21° β=135.48° γ=97.15° Z=2 chlorosulfate; moisture sensitive [18][19]
CaB
2S
4O
16 		monoclinic P21/c a=5.5188, b=15.1288, c=13.2660;

β=92.88°

sheet [4]
Mn[B
2(SO
4)
4] 		monoclinic P21/n a=8.0435, b=7.9174, c=9.3082;

β=110.94° Z=2

553.63 colourless [20]
α-Mn
4[B
2O(SO
4)
6] 		833.74 trigonal P3 a=8.1086, c=7.7509;

Z=1

441.3 3.137 colourless [6]
β-Mn
4[B
2O(SO
4)
6] 		833.74 trigonal P3 a=13.9196 c=7.4854
α-Co
4[B
2O(SO
4)
6] 		monoclinic C2/c a=17.4254, b=5.3397, c=14.3214;

β=126.03°; Z=4

269.40 2.860 pink [16]
β-Co
4[B
2O(SO
4)
6] 		monoclinic P21/n a=7.8892, b=8.1042, c= 9.0409;

β=111.29°; Z=2

269.29 2.803 pink [16]
α-Co
4[B
2O(SO
4)
6] 		849.70 trigonal P3 a=7.991, c=7.669;

Z=1

418.0 3.376 pink [6]
α-Ni
4[B
2O(SO
4)
6] 		848.82 trigonal P3 a=7.9359 c=7.4398 Z=1 405.77 3.474 yellow [6]
Cu[B(SO
4)
2(HSO
4)] 		triclinic P1 a=5.3096, b=7.0752, c=11.1977;

α=81.154°, β=80.302°, γ=80.897°

cyclic [4]
Cu[B
2(SO
4)
4] 		triclinic P1 a=5.2470, b=7.1371, c=7.9222;

α=73.814°, β=70.692°, γ=86.642°

chain [4]
Zn[B
2(SO
4)
4] 		monoclinic P21/n a=8.0435, b=7.9174, c=9.3082;

β=111.26°; Z=2

534.36 colourless [20]
α-Zn
4[B
2O(SO
4)
6] 		875.46 trigonal P3 a=7.9971, c=7.4895;

Z=1

414.81 3.505 colourless [6]
Rb[B(SO4)2] tetragonal P4/ncc a = 9.1823 c = 7.4559 Z = 4 628.64 3.05 [18]
Rb
2B
4SO
10 		406.24 monoclinic C2 a=11.3127, b=6.5152, c=12.971;

β=105.411°; Z=4

921.6 2.928 colourless [17]
Rb
3[B(SO
4)
3] 		orthorhombic Ibca a=7.2759, b=14.794, c=22.637 [10]
Rb
4[B
2O(SO
4)
4] 		orthorhombic Pnma a=8.0415, b=10.647, c=20.425 [4]
Rb
5[B(SO
4)
4] 		tetragonal P43212 a=10.148, c=16.689;

Z=4

band gap 3.99 eV [4][21]
Rb
3HB
4S
2O
14 		P63/m a=6.502, c=19.02;

Z=2

[22]
Rb
3H
2[BOB(PO
4)
3] 		white [13]
LiRb
4[B(SO
4)
4] 		743.8 monoclinic P21 a=7.5551, c=14.560, c=7.5517;

β=90.2372°; Z=2

transparent [23]
LiRb
4[B(SO
4)
4] 		743.8 tetragonal I4 a=7.6128, c=14.631;

Z=2

at 500K [23]
Sr[B
2(SO
4)
4] 		493.48 orthorhombic Pnma a=12.574, b=12.421, c=7.319;

Z=4

1143.1 2.867 decomposes 400 °C (752 °F) [8][2]
Sr[B
2(SO
4)
3(S
2O
7)] 		573.54 monoclinic P21/n a=7.470, b=15.334, c=12.220;

β=93.29°; Z=4

1397.5 2.726 [8]
Sr[B
2O(SO
4)
3] 		orthorhombic Pnma a=1657.3, b=12.037, c=4.39484 [8][4]
Sr[B
3O(SO
4)
4(SO
4H)] 		617.36 monoclinic P21/c a=11.3309, b=7.1482, c=19.355;

β=106.878°; Z=4

1500.1 2.73 colourless; Sr in 9 coordination by sulfate oxygens [24]
Y
2[B
2(SO
4)
6] 		monoclinic C2/c a=13.5172, b=11.3941, c=10.8994;

β=93.447°

cyclic [14][4]
Pd[B(S
2O
7)
2]
2 		monoclinic P21/c a=7.2686, b=12.7802, c=11.4930;

β=101.343°; Z=2

1046.8 2.64 blue [25]
Pd[B(S
2O
7)
2]
2 		tetragonal P41 a=13.8210, c=21.724;

Z=8

4149.7 2.66 blue [25]
Pd[B(SO
4)(S
2O
7)]
2 		monoclinic P21/c a = 6.7061 b = 16.0198 c = 8.1681 β = 94.923° Z = 2 874.27 2.55 red [25]
Ag[B(SO4)2] P4/ncc a=8.6679 c=7.2897 [4]
Ag[B(S2O7)2] monoclinic P21/c a = 9.507, b = 9.601, c = 11.730, β = 98.35° Z=4 1059.3 2.953 colourless [26]
Cd[B2(SO4)4] [27]
Cd[B2O(SO4)3] 438.20 orthorhombic Pnma a=8.9692 b=11.520 c=8.7275 Z=4 901.8 3.23 colourless [27]
Cd4[B2O(SO4)6] trigonal P3 a=8.2222 c=7.9788 Z=1 467.14 3.78 colourless [27]
(I4)[B(S2O7)2]2 triclinic P1 a = 11.3714 b = 11.5509 c = 12.7811 α = 68.638° β = 68.275° γ = 64.626° Z=2 1366.16 2.999 orange-brown [28]
Cs2B4SO10 501.12 monoclinic C2 a=11.4012 b=6.5997 c=13.5702 β=103.934° Z=4 919.04 3.359 colourless [17]
Cs2[B2O(SO4)3] monoclinic P2/c a=14.765 b=6.710 c=12.528 β=104.50 [22]
Cs3HB4S2O14 P63/m a = 6.5648, c = 19.5669 Z=2 [22]
Cs3H2[BOB(PO4)3] monoclinic P21/c a=8.2436 b=6.7387 c=24.414 β=92.713° Z=4 1354.7 3.538 proton conductor [13]
Cs[B(SO4)(S2O7)] monoclinic P21/c a=10.4525, b=11.319, c=8.2760; β=103.206; Z=4 [8][9]
Cs3Li2[B(SO4)4] monoclinic P21/n a=13.7698 c=8.2376 c=13.9066 β=91.778 [14][4]
Cs3Na2[B(SO4)4] monoclinic P21/c a=13.6406 b=7.9475 c=13.9573 β=990.781 [14][4]
CsK4[B(SO4)4] P43212 a=9.9433 c=16.881 [14][4]
Ba[B2(SO4)4] orthorhombic Pnna a = 12.791, b = 12.800, c = 7.317 Z = 4 [8][29]
Ba[B2O(SO4)3] orthorhombic Pnma a=17.1848 b=12.3805 c=4.4226 [8]
Ba[B(S2O7)2]2 monoclinic I2/a a = 11.6077, b = 8.9144, c = 21.303, β = 104.034° Z = 4 chains [8][29]
La2[B2(SO4)6] monoclinic C2/c a=1379.2 b=1158.9 c=1139.5 β=93.611 cyclic [14][4]
Ce2[B2(SO4)6] monoclinic C2/c 13.740 b=11.5371 c=11.3057 β=93.661 cyclic [14][4]
Pr2[B2(SO4)6] monoclinic C2/c a=13.711 b=11.5305 c=11.2643 β=93.668 cyclic [14][4]
Nd2[B2(SO4)6] monoclinic C2/c a=13.6775 b=11.51.34 11.2046 β=93.5909 cyclic [14][4]
Sm2[B2(SO4)6] monoclinic C2/c a=13.633 b=11.492 c=11.112 β=93.567 cyclic [14][4]
Eu2[B2(SO4)6] monoclinic C2/c a=13.602 b=11.470 c=11.050 β=93.465 cyclic [14][4]
Gd2[B2(SO4)6] monoclinic C2/c a=13.5697 b=11.4426 c=11.0271 β= cyclic [14][4]
Tb2[B2(SO4)6] monoclinic C2/c a=13.5601 b=11.42.48 c=10.9881 β=93.534 cyclic [14][4]
Dy2[B2(SO4)6] monoclinic C2/c a=13.568 b=11.425 c=10.9703 β=93.540 cyclic [14][4]
Ho2[B2(SO4)6] monoclinic C2/c a=13.505 b=11.409 c=10.921 β=93.453 cyclic [14][4]
Er2[B2(SO4)6] monoclinic C2/c a=13.551 b=11.411 c=10.882 β=93.41 cyclic [14][4]
Tm2[B2(SO4)6] monoclinic C2/c a=13.4981 b=11.3617 10.8327 β=93.4500 cyclic [14][4]
Yb2[B2(SO4)6] monoclinic C2/c a=13.495 b=11.3452 c=10.7961 β=93.390 cyclic [14][4]
Lu2[B2(SO4)6] monoclinic C2/c a=13.469 b=11.364 c=10.799 β=93.369 cyclic [14][4]
[Au3Cl4][B(S2O7)2] monoclinic P21/c a=10.6266 b=12.7938 c=12.7373 β=99.322° Z=4 1708.82 4.259 yellow [25][30]
[Au2Cl4][B(S2O7)2](SO3) orthorhombic Fddd a=13.1467, b=17.8576 c=31.711 Z=16 7444.8 3.49 metallic grey or transparent green dependent on polarization [25][30]
Pb[B2(SO4)4] 613.05 orthorhombic Pnna a=12.516 b=12.521 c=7.302 Z=4 114.43 3.558 loop chain [4][31]
Pb[B2O(SO4)3] orthorhombic P21/m a=4.4000 b=12.1019 c=8.6043 [4]
Bi2[B2(SO4)6] 659.08 orthorhombic C2/c a = 13.568, b = 11.490, c = 11.106 Z=4 1728.8 3.894 [14]
(H3O)Bi[B(SO4)2]4 1039.72 I4 a=11.857, c=8.149 Z=2 1156.84 2.99 colourless; non-linear optical [14]
(UO2)[B(SO4)2(SO3OH)] 569.52 triclinic P1 a=5.448 b=7.021 c=13.522 α =92.248° β =95.347° γ =101.987° Z=2 3.762 green [32]
(UO2)2[B2O(SO4)3(SO3OH)2] 1058.23 monoclinic P21/n a=10.872 b=11.383 c=14.812 β=92.481 Z=4 3.838 yellow [32]

References

  1. ↑ 1.0 1.1 Höppe, Henning A.; Kazmierczak, Karolina; Daub, Michael; Förg, Katharina; Fuchs, Franziska; Hillebrecht, Harald (2012-06-18). "The First Borosulfate K5[B(SO4)4"] (in en). Angewandte Chemie International Edition 51 (25): 6255–6257. doi:10.1002/anie.201109237. PMID 22566359. Bibcode: 2012ACIE...51.6255H. http://doi.wiley.com/10.1002/anie.201109237. 
  2. ↑ 2.0 2.1 2.2 Netzsch, Philip; Höppe, Henning A. (2020-09-30). "Synthesis and Characterization of the Chain Borosulfates (NH4)3[B(SO4)3] and Sr[B2(SO4)4]" (in en). Zeitschrift für anorganische und allgemeine Chemie 646 (18): 1563–1569. doi:10.1002/zaac.202000105. ISSN 0044-2313. Bibcode: 2020ZAACh.646.1563N. 
  3. ↑ Schott, G.; Kibbel, H. U. (1962). "Über Sulfatoborate" (in en). Zeitschrift für anorganische und allgemeine Chemie 314 (1–2): 104–112. doi:10.1002/zaac.19623140113. ISSN 0044-2313. Bibcode: 1962ZAACh.314..104S. https://onlinelibrary.wiley.com/doi/10.1002/zaac.19623140113. 
  4. ↑ 4.00 4.01 4.02 4.03 4.04 4.05 4.06 4.07 4.08 4.09 4.10 4.11 4.12 4.13 4.14 4.15 4.16 4.17 4.18 4.19 4.20 4.21 4.22 4.23 4.24 4.25 4.26 4.27 4.28 4.29 4.30 4.31 4.32 4.33 Bruns, Jörn; Höppe, Henning A.; Daub, Michael; Hillebrecht, Harald; Huppertz, Hubert (2020-06-26). "Borosulfates—Synthesis and Structural Chemistry of Silicate Analogue Compounds" (in en). Chemistry – A European Journal 26 (36): 7966–7980. doi:10.1002/chem.201905449. ISSN 0947-6539. PMID 31943390. Bibcode: 2020ChEuJ..26.7966B. 
  5. ↑ Kong, Fang; Ma, Yunxiang; Mao, Jianggao (January 2018). "Lanthanide Inorganic Solids Based on Main Group Borates and Oxyanions of Lone Pair Cations: Lanthanide Inorganic Solids Based on Main Group Borates and Oxyanions of Lone Pair Cations" (in en). Chinese Journal of Chemistry 36 (1): 63–72. doi:10.1002/cjoc.201700597. http://doi.wiley.com/10.1002/cjoc.201700597. 
  6. ↑ 6.0 6.1 6.2 6.3 6.4 6.5 6.6 6.7 Netzsch, Philip; Gross, Peter; Takahashi, Hirotaka; Höppe, Henning A. (2018-07-16). "Synthesis and Characterization of the First Borosulfates of Magnesium, Manganese, Cobalt, Nickel, and Zinc" (in en). Inorganic Chemistry 57 (14): 8530–8539. doi:10.1021/acs.inorgchem.8b01234. ISSN 0020-1669. PMID 29957944. https://pubs.acs.org/doi/10.1021/acs.inorgchem.8b01234. 
  7. ↑ Logemann, Christian; Wickleder, Mathias S. (2013-12-23). "B2S2O9: A Boron Sulfate with Phyllosilicate Topology" (in en). Angewandte Chemie International Edition 52 (52): 14229–14232. doi:10.1002/anie.201307056. PMID 24214383. Bibcode: 2013ACIE...5214229L. http://doi.wiley.com/10.1002/anie.201307056. 
  8. ↑ 8.00 8.01 8.02 8.03 8.04 8.05 8.06 8.07 8.08 8.09 8.10 8.11 8.12 8.13 8.14 Netzsch, Philip; Höppe, Henning A. (2020-11-26). "Sr[B2(SO4)3(S2O7): A Borosulfate with an Unprecedented Chain Structure Comprising Disulfate Groups"] (in en). Inorganic Chemistry 59 (24): 18102–18108. doi:10.1021/acs.inorgchem.0c02560. ISSN 0020-1669. PMID 33241934. https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c02560. 
  9. ↑ 9.0 9.1 9.2 9.3 9.4 Daub, Michael; Kazmierczak, Karolina; Höppe, Henning A.; Hillebrecht, Harald (2013). "The Borosulfate Story Goes on—From Alkali and Oxonium Salts to Polyacids" (in en). Chemistry – A European Journal 19 (50): 16954–16962. doi:10.1002/chem.201303012. ISSN 1521-3765. PMID 24203813. Bibcode: 2013ChEuJ..1916954D. https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/chem.201303012. 
  10. ↑ 10.0 10.1 10.2 10.3 10.4 10.5 Daub, Michael; Kazmierczak, Karolina; Gross, Peter; Höppe, Henning; Hillebrecht, Harald (2013-05-20). "Exploring a New Structure Family: Alkali Borosulfates Na5[B(SO4)4, A3[B(SO4)3] (A = K, Rb), Li[B(SO4)2], and Li[B(S2O7)2]"] (in en). Inorganic Chemistry 52 (10): 6011–6020. doi:10.1021/ic400267s. ISSN 0020-1669. PMID 23656591. https://pubs.acs.org/doi/10.1021/ic400267s. 
  11. ↑ Sutorius, Stefan; Hanrath, Michael; Bruns, Jörn (2022-02-09). "Be[B2(SO4)4] – A Borosulfate exhibiting Ino- and Phyllosilicate Analogue Topology" (in en). European Journal of Inorganic Chemistry 2022 (11). doi:10.1002/ejic.202200009. ISSN 1434-1948. Bibcode: 2022EJIC.2022E0009S. 
  12. ↑ Li, Zijian; Jin, Wenqi; Zhang, Fangfang; Chen, Zilong; Yang, Zhihua; Pan, Shilie (2021-10-09). "Achieving Short-Wavelength Phase-Matching Second Harmonic Generation in Boron-Rich Borosulfate with Planar [BO3 Units"] (in en). Angewandte Chemie International Edition 61 (4). doi:10.1002/anie.202112844. ISSN 1433-7851. PMID 34626043. https://onlinelibrary.wiley.com/doi/10.1002/anie.202112844. 
  13. ↑ 13.0 13.1 13.2 13.3 Ridenour, J. August; Chaloux, Brian L.; Johannes, Michelle D.; Bernstein, Noam; Finn, Matthew T.; Ryou, Heonjune; Epshteyn, Albert (2025-08-01). "Cs3H2[BOB(PO4)3 - the Best-Performing 1D Borophosphate Intermediate Temperature Proton Electrolyte"] (in en). ACS Omega. doi:10.1021/acsomega.5c04320. ISSN 2470-1343. https://pubs.acs.org/doi/10.1021/acsomega.5c04320. 
  14. ↑ 14.00 14.01 14.02 14.03 14.04 14.05 14.06 14.07 14.08 14.09 14.10 14.11 14.12 14.13 14.14 14.15 14.16 14.17 14.18 14.19 14.20 Hämmer, Matthias; Bayarjargal, Lkhamsuren; Höppe, Henning A. (2020-11-12). "The First Bismuth Borosulfates Comprising Oxonium and a Tectosilicate-Analogous Anion" (in en). Angewandte Chemie International Edition 60 (3): 1503–1506. doi:10.1002/anie.202011786. ISSN 1433-7851. PMID 33026134. open access
  15. ↑ 15.0 15.1 15.2 Fan, Jinbin; Yan, Ziting; Chen, Zilong; Li, Huimin; Yang, Zhihua; Zhang, Fangfang; Pan, Shilie (2024-08-19). "Na2B6SO13 with unprecedented [B6SO13∞ double chains and largest birefringence among borosulfates induced by the uniform arrangement of [B3O7] units"] (in en). Science China Chemistry 68 (2): 475–480. doi:10.1007/s11426-024-2170-6. ISSN 1674-7291. https://link.springer.com/10.1007/s11426-024-2170-6. 
  16. ↑ 16.0 16.1 16.2 Netzsch, Philip; Pielnhofer, Florian; Glaum, Robert; Höppe, Henning A. (2020-11-17). "Synthesis-Controlled Polymorphism and Optical Properties of Phyllosilicate-Analogous Borosulfates M[B2(SO4)4 (M =Mg, Co)"] (in en). Chemistry – A European Journal 26 (64): 14745–14753. doi:10.1002/chem.202003214. ISSN 0947-6539. PMID 32744744. 
  17. ↑ 17.0 17.1 17.2 Li, Zijian; Jin, Wenqi; Zhang, Fangfang; Yang, Zhihua; Pan, Shilie (2022-11-23). "Exploring Short-Wavelength Phase-Matching Nonlinear Optical Crystals by Employing KBe2BO3F2 as the Template" (in en). ACS Central Science 8 (11): 1557–1564. doi:10.1021/acscentsci.2c00832. ISSN 2374-7943. PMID 36439311. 
  18. ↑ 18.0 18.1 Nickelsen, Jasper; Edelmann, Arthur; Symeonidis, Marios; Bruns, Jörn (2025-10-11). "Synthesis and Crystal Structure of Rb[B(SO 4 ) 2 : A Borosulfate Obtained from a Reaction with Chlorosulfuric Acid"] (in en). Zeitschrift für anorganische und allgemeine Chemie. doi:10.1002/zaac.202500156. ISSN 0044-2313. https://onlinelibrary.wiley.com/doi/10.1002/zaac.202500156. 
  19. ↑ Mairesse, G.; Drache, M. (1978-06-01). "The crystal structure of potassium tetrachlorosulfatoborate, K[B(SO 3 Cl) 4 "]. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry 34 (6): 1771–1776. doi:10.1107/S0567740878006676. ISSN 0567-7408. https://journals.iucr.org/paper?S0567740878006676. 
  20. ↑ 20.0 20.1 Pasqualini, Leonard C.; Huppertz, Hubert; Bruns, Jörn (2019-12-17). "M[B2(SO4)4] (M = Mn, Zn)—Syntheses and Crystal Structures of Two New Phyllosilicate Analogue Borosulfates" (in en). Inorganics 7 (12): 145. doi:10.3390/inorganics7120145. ISSN 2304-6740. 
  21. ↑ Dong, Lingyun; Pan, Shilie; Wang, Ying; Yu, Hongwei; Lin, Xiaoxia; Han, Shujuan (March 2015). "Synthesis and structural characterization of a new rubidium borosulfate, Rb5BS4O16" (in en). Materials Research Bulletin 63: 93–98. doi:10.1016/j.materresbull.2014.11.047. https://linkinghub.elsevier.com/retrieve/pii/S0025540814007363. 
  22. ↑ 22.0 22.1 22.2 Daub, Michael; Hillebrecht, Harald (September 2015). "Borosulfates Cs2B2S3O13, Rb4B2S4O17, and A3HB4S2O14 (A = Rb, Cs) – Crystalline Approximants for Vitreous B2O3?" (in en). European Journal of Inorganic Chemistry 2015 (25): 4176–4181. doi:10.1002/ejic.201500603. ISSN 1434-1948. Bibcode: 2015EJIC.2015.4176D. https://onlinelibrary.wiley.com/doi/10.1002/ejic.201500603. 
  23. ↑ 23.0 23.1 Li, Yanqiang; Zhou, Zhengyang; Zhao, Sangen; Liang, Fei; Ding, Qingran; Sun, Junliang; Lin, Zheshuai; Hong, Maochun et al. (2021-03-08). "A Deep-UV Nonlinear Optical Borosulfate with Incommensurate Modulations" (in en). Angewandte Chemie International Edition 60 (20): 11457–11463. doi:10.1002/anie.202102107. ISSN 1433-7851. PMID 33686736. Bibcode: 2021ACIE...6011457L. https://onlinelibrary.wiley.com/doi/10.1002/anie.202102107. 
  24. ↑ Pasqualini, Leonard; Huppertz, Hubert; Je, Minyeong; Choi, Heechae; Bruns, Jörn (2021-06-13). "Triple Vertex Linkage of (BO4)-Tetrahedra in a Borosulfate: Synthesis, Crystal Structure, and Quantum Chemical Investigation of Sr[B3O(SO4)4(SO4H)"] (in en). Angewandte Chemie International Edition 60 (36): 19740–19743. doi:10.1002/anie.202106337. ISSN 1433-7851. PMID 34121302. 
  25. ↑ 25.0 25.1 25.2 25.3 25.4 Sutorius, Stefan; Patrun, David; Edelmann, Arthur; Schumacher, Lars; Pöttgen, Rainer; Suta, Markus; Bruns, Jörn (2025-07-25). "Pd[B(S2O7)22 and Pd[B(SO4)(S2O7)]2: Two Borosulfates with Pd2+ in Octahedral and One with Pd2+ in Square Planar Oxygen Coordination"] (in en). Chemistry – A European Journal 31 (42). doi:10.1002/chem.202501515. ISSN 0947-6539. PMID 40454746. https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202501515. 
  26. ↑ Netzsch, Philip; Höppe, Henning A. (2020-12-29). "Ag[B(S2O7)2]: The First Transition Metal Borosulfate Featuring Disulfate Groups" (in en). European Journal of Inorganic Chemistry 2021 (11): 1065–1070. doi:10.1002/ejic.202001095. ISSN 1434-1948. 
  27. ↑ 27.0 27.1 27.2 Hämmer, Matthias; Höppe, Henning A. (2022-09-02). "The Unconventional Cadmium Borosulfates Cd[B2O(SO4)3] and Cd4[B2O(SO4)6]" (in en). Zeitschrift für anorganische und allgemeine Chemie 648 (21). doi:10.1002/zaac.202200197. ISSN 0044-2313. Bibcode: 2022ZAACh.648E0197H. 
  28. ↑ van Gerven, David; Sutorius, Stefan; Bruns, Jörn; Wickleder, Mathias S. (2022-07-20). "Stabilizing the Homopolycation (I4)2+ with a Hexasulfate in (I4)[S6O19 and a Borosulfate in (I4)[B(S2O7)2]2"] (in en). ChemistryOpen 11 (11). doi:10.1002/open.202200122. ISSN 2191-1363. PMID 35856862. 
  29. ↑ 29.0 29.1 Netzsch, Philip; Pielnhofer, Florian; Höppe, Henning A. (2020-10-19). "From S–O–S to B–O–S to B–O–B Bridges: Ba[B(S2O7)22 as a Model System for the Structural Diversity in Borosulfate Chemistry"] (in en). Inorganic Chemistry 59 (20): 15180–15188. doi:10.1021/acs.inorgchem.0c02156. ISSN 0020-1669. PMID 33001636. https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c02156. 
  30. ↑ 30.0 30.1 Sutorius, Stefan; van Gerven, David; Olthof, Selina; Rasche, Bertold; Bruns, Jörn (2022-04-19). "Polycations Stabilised by Borosulfates: [Au3Cl4[B(S2O7)2] and the One-Dimensional Metal [Au2Cl4][B(S2O7)2](SO3)"] (in en). Chemistry – A European Journal 28 (22). doi:10.1002/chem.202200004. ISSN 0947-6539. PMID 35262987. Bibcode: 2022ChEuJ..28E0004S. 
  31. ↑ Schönegger, Sandra; Bruns, Jörn; Gartner, Benjamin; Wurst, Klaus; Huppertz, Hubert (2018-12-31). "Synthesis and Characterization of the First Lead(II) Borosulfate Pb[B2(SO4)4]: Synthesis and Characterization of the First Lead(II) Borosulfate Pb[B2(SO4)4]" (in en). Zeitschrift für anorganische und allgemeine Chemie 644 (24): 1702–1706. doi:10.1002/zaac.201800130. 
  32. ↑ 32.0 32.1 Sweet, Teagan F. M.; Felton, Daniel E.; Szymanowski, Jennifer E. S.; Burns, Peter C. (2022-09-01). "Targeting Diverse Bridging Motifs within Actinide Borosulfates and Establishing an Unconventional Structural Hierarchy" (in en). Inorganic Chemistry 61 (40): 15953–15960. doi:10.1021/acs.inorgchem.2c02144. ISSN 0020-1669. PMID 36047685. https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c02144. 

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