Borosulfate Explained

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] although the compound class as such had been postulated already in 1962 by G. Schott and H. U. Kibbel.^[2] 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, and also boroantimonates, borogallates, borogermanates, borophosphates, boroselenites and borosilicates.^[3]

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.

List

	chem	mw	crystal system	space group	unit cell Å	volume	density	comment	references
boron sulfate	B2S2O9	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	^[4]
	H[B(HSO<sub>4</sub>)<sub>4</sub>]		monoclinic	P21/c	a=15.6974, b=11.436, c=8.5557; β=90.334°; Z=8			superacid	^[5]
	H3O[B(SO<sub>4</sub>)<sub>2</sub>]			P4/ncc	a=9.1377, c=7.3423; Z=4
	H[B(SO<sub>4</sub>)(S<sub>2</sub>O<sub>7</sub>)]		monoclinic	P21/c	a=15.697 b=11.4362 c=8.5557 β=90.334
	Li[B(SO<sub>4</sub>)<sub>2</sub>]			Pc	a = 7.635, b = 9.342, c = 8.432, and β = 92.55°			3D network, like tectosilicate	^[6]
	Li[B(S<sub>2</sub>O<sub>7</sub>)<sub>2</sub>]		orthorhombic	P212121	a = 10.862, b = 10.877, c = 17.769
	Li5[B(SO<sub>4</sub>)<sub>4</sub>]		orthorhombic	P21/c	a=8.0191 b=10.2111 c=15.0401				^[7]
	Be[B<sub>2</sub>(SO<sub>4</sub>)<sub>4</sub>]		monoclinic	C2/c	a= 23.856, b= 7.3507, c= 12.3235, β= 98.724(2)°, Z=8	2136.1	2.58	colourless	^[8]
	NH4[B(SO<sub>4</sub>)<sub>2</sub>]			P4/ncc	a=9.1980 c=7.2458			decompose 320 °C, proton conductor	^[9]
	NH4[B(S<sub>2</sub>O<sub>7</sub>)<sub>2</sub>]		monoclinic	Cc	a=11.4403 b=14.9439 c=13.8693 β=93.662
	(NH4)2B4SO10	271.38	monoclinic	C2	a=11.3685 b=6.5541 c=12.8328 β=106.247 4	918.0	1.964	SHG 1.1 × KDP; min PM wavelength 252 nm; decompose 300 °C	^[10]
	[NH<sub>4</sub>]3[B(SO<sub>4</sub>)<sub>3</sub>]	343.12	orthorhombic	Ibca	a=7.2858 b=14.7048 c=22.7052 Z=8	2433.2	1.928	decompose 320 °C chains	^[11]
	Na[B(SO<sub>4</sub>)<sub>2</sub>]		monoclinic	P2/c	a=5.434 b=7.570 c=7.766 β=99.74
	Na[B(S<sub>2</sub>O<sub>7</sub>)<sub>2</sub>]		monoclinic	P21/c	a=10.949, b=8.49, c=12.701; β=110.227°; Z=4
	Na5[B(SO<sub>4</sub>)<sub>4</sub>]-I		orthorhombic	Pca21	a = 10.730, b = 13.891, c = 18.197
	Na5[B(SO<sub>4</sub>)<sub>4</sub>]-II		orthorhombic	P212121	a = 8.624, b = 9.275, c = 16.671
	α-Mg4[B<sub>2</sub>O(SO<sub>4</sub>)<sub>6</sub>]	711.22	trigonal	P	a=8.0165 c=7.4858 Z=1	416.62	2.835	colourless	^[12]
	β-Mg4[B<sub>2</sub>O(SO<sub>4</sub>)<sub>6</sub>]	711.22	hexagonal	P	a = 13.9196, c = 7.4854, Z = 3	1253	2.821	colourless
	Mg[B<sub>2</sub>(SO<sub>4</sub>)<sub>4</sub>]	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 decompose 550 °C
	β-Mg[B<sub>2</sub>(SO<sub>4</sub>)<sub>4</sub>]		monoclinic	P21/n	a=7.9100 b=8.0815 c=9.0376 β=111.37° Z=2	269.01	2.667	colourless decompose 550 °C	^[13]
	K[B(SO<sub>4</sub>)<sub>2</sub>]			P4/ncc	a=8.9739 c=7.4114
	K[B(S<sub>2</sub>O<sub>7</sub>)<sub>2</sub>]		monoclinic	Cc	a=11.3368, b=14.66, c=13.6650; β=94.235°; Z=8
	K2B4SO10	313.50	monoclinic	C2	a=11.2631 b=6.4339 c=12.649 β=105.707° Z=4	882.4	2.360	colourless	^[14]
pentapotassium borosulfate	K5[B(SO<sub>4</sub>)<sub>4</sub>]			P41	a=9.9023 c=16.1871	1687.2	2.471	first discovered	^[15]
	K3[B(SO<sub>4</sub>)<sub>3</sub>]		orthorhombic	Ibca	a = 7.074, b = 14.266, c = 22.58
	K4[BS<sub>4</sub>O<sub>15</sub>(OH)]		monoclinic	I2/a	a=14.524 b=7.3916 c=15.7857 β=115.50
	CaB2S4O16		monoclinic	P21/c	a=5.5188 b=15.1288 c=13.2660 β=92.88			sheet
	Mn[B<sub>2</sub>(SO<sub>4</sub>)<sub>4</sub>]		monoclinic	P21/n	a = 8.0435, b = 7.9174, c = 9.3082, β = 110.94° Z=2	553.63		colourless	^[16]
	α-Mn4[B<sub>2</sub>O(SO<sub>4</sub>)<sub>6</sub>]	833.74	trigonal	P	a=8.1086 c=7.7509 Z=1	441.3	3.137	colourless
	β-Mn4[B<sub>2</sub>O(SO<sub>4</sub>)<sub>6</sub>]	833.74	trigonal	P	a=13.9196 c=7.4854
	α-Co[B<sub>2</sub>(SO<sub>4</sub>)<sub>4</sub>]		monoclinic	C2/c	a=17.4254 b=5.3397 c=14.3214 β=126.03° Z=4	269.40	2.860	pink
	β-Co[B<sub>2</sub>(SO<sub>4</sub>)<sub>4</sub>]		monoclinic	P21/n	a=7.8892 b=8.1042 c= 9.0409 β=111.29° Z=2	269.29	2.803	pink
	α-Co4[B<sub>2</sub>O(SO<sub>4</sub>)<sub>6</sub>]	849.70	trigonal	P	a=7.991 c=7.669 Z=1	418.0	3.376	pink
	α-Ni4[B<sub>2</sub>O(SO<sub>4</sub>)<sub>6</sub>]	848.82	trigonal	P	a=7.9359 c=7.4398 Z=1	405.77	3.474	yellow
	Cu[B(SO<sub>4</sub>)<sub>2</sub>(HSO<sub>4</sub>)]		triclinic	P	a=5.3096 b=7.0752 c=11.1977 α=81.154 β=80.302 γ=80.897			cyclic
	Cu[B<sub>2</sub>(SO<sub>4</sub>)<sub>4</sub>]		triclinic	P	a=5.2470 b=7.1371 c=7.9222 α=73.814 β=70.692 γ=86.642			chain
	Zn[B<sub>2</sub>(SO<sub>4</sub>)<sub>4</sub>]		monoclinic	P21/n	a = 8.0435, b = 7.9174, c = 9.3082, β = 111.26° Z=2	534.36		colourless
	α-Zn4[B<sub>2</sub>O(SO<sub>4</sub>)<sub>6</sub>]	875.46	trigonal	P	a=7.9971 c=7.4895 Z=1	414.81	3.505	colourless
	Rb2B4SO10	406.24	monoclinic	C2	a=11.3127 b=6.5152 c=12.971 β=105.411° Z=4	921.6	2.928	colourless
	Rb3[B(SO<sub>4</sub>)<sub>3</sub>]		orthorhombic	Ibca	a = 7.2759, b = 14.794, c = 22.637
	Rb4[B<sub>2</sub>O(SO<sub>4</sub>)<sub>4</sub>]		orthorhombic	Pnma	a=8.0415 b=10.647 c=20.425
	Rb5[B(SO<sub>4</sub>)<sub>4</sub>]		tetragonal	P43212	a=10.148 c=16.689 Z=4			band gap 3.99 eV	^[17]
	Rb3HB4S2O14			P63/m	a = 6.502, c = 19.02 Z=2				^[18]
	LiRb4[B(SO<sub>4</sub>)<sub>4</sub>]	743.8	monoclinic		a=7.5551, c=14.560, c=7.5517 β=90.2372 Z=2			transparent	^[19]
	LiRb4[B(SO<sub>4</sub>)<sub>4</sub>]	743.8	tetragonal	I	a=7.6128, c=14.631, Z=2			at 500K
	Sr[B<sub>2</sub>(SO<sub>4</sub>)<sub>4</sub>]	493.48	orthorhombic	Pnma	a=12.574 b=12.421 c=7.319 Z=4	1143.1	2.867	decompose 400 °C
	Sr[B<sub>2</sub>(SO<sub>4</sub>)<sub>3</sub>(S<sub>2</sub>O<sub>7</sub>)]	573.54	monoclinic	P21/n	a = 7.470, b = 15.334, c = 12.220, β = 93.29° Z=4	1397.5	2.726		^[20]
	Sr[B<sub>2</sub>O(SO<sub>4</sub>)<sub>3</sub>]		orthorhombic	Pnma	a=1657.3 b=12.037 c=4.39484
	Sr[B<sub>3</sub>O(SO<sub>4</sub>)<sub>4</sub>(SO<sub>4</sub>H)]	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	^[21]
	Y2[B<sub>2</sub>(SO<sub>4</sub>)<sub>6</sub>]		monoclinic	C2/c	a=13.5172 b=11.3941 c=10.8994 β=93.447			cyclic
	Ag[B(SO<sub>4</sub>)<sub>2</sub>]			P4/ncc	a=8.6679 c=7.2897
	Ag[B(S<sub>2</sub>O<sub>7</sub>)<sub>2</sub>]		monoclinic	P21/c	a = 9.507, b = 9.601, c = 11.730, β = 98.35° Z=4	1059.3	2.953	colourless	^[22]
	Cd[B<sub>2</sub>(SO<sub>4</sub>)<sub>4</sub>]								^[23]
	Cd[B<sub>2</sub>O(SO<sub>4</sub>)<sub>3</sub>]	438.20	orthorhombic	Pnma	a=8.9692 b=11.520 c=8.7275 Z=4	901.8	3.23	colourless
	Cd4[B<sub>2</sub>O(SO<sub>4</sub>)<sub>6</sub>]		trigonal	P	a=8.2222 c=7.9788 Z=1	467.14	3.78	colourless
	(I4)[B(S<sub>2</sub>O<sub>7</sub>)<sub>2</sub>]2		triclinic	P	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	^[24]
	Cs2B4SO10	501.12	monoclinic	C2	a=11.4012 b=6.5997 c=13.5702 β=103.934° Z=4	919.04	3.359	colourless
	Cs2[B<sub>2</sub>O(SO<sub>4</sub>)<sub>3</sub>]		monoclinic	P2/c	a=14.765 b=6.710 c=12.528 β=104.50
	Cs3HB4S2O14			P63/m	a = 6.5648, c = 19.5669 Z=2
	Cs[B(SO<sub>4</sub>)(S<sub>2</sub>O<sub>7</sub>)]		monoclinic	P21/c	a=10.4525, b=11.319, c=8.2760; β=103.206; Z=4
	Cs3Li2[B(SO<sub>4</sub>)<sub>4</sub>]		monoclinic	P21/n	a=13.7698 c=8.2376 c=13.9066 β=91.778
	Cs3Na2[B(SO<sub>4</sub>)<sub>4</sub>]		monoclinic	P21/c	a=13.6406 b=7.9475 c=13.9573 β=990.781
	CsK4[B(SO<sub>4</sub>)<sub>4</sub>]			P43212	a=9.9433 c=16.881
	Ba[B<sub>2</sub>(SO<sub>4</sub>)<sub>4</sub>]		orthorhombic	Pnna	a = 12.791, b = 12.800, c = 7.317 Z = 4				^[25]
	Ba[B<sub>2</sub>O(SO<sub>4</sub>)<sub>3</sub>]		orthorhombic	Pnma	a=17.1848 b=12.3805 c=4.4226
	Ba[B(S<sub>2</sub>O<sub>7</sub>)<sub>2</sub>]2		monoclinic	I2/a	a = 11.6077, b = 8.9144, c = 21.303, β = 104.034° Z = 4			chains
	La2[B<sub>2</sub>(SO<sub>4</sub>)<sub>6</sub>]		monoclinic	C2/c	a=1379.2 b=1158.9 c=1139.5 β=93.611			cyclic
	Ce2[B<sub>2</sub>(SO<sub>4</sub>)<sub>6</sub>]		monoclinic	C2/c	13.740 b=11.5371 c=11.3057 β=93.661			cyclic
	Pr2[B<sub>2</sub>(SO<sub>4</sub>)<sub>6</sub>]		monoclinic	C2/c	a=13.711 b=11.5305 c=11.2643 β=93.668			cyclic
	Nd2[B<sub>2</sub>(SO<sub>4</sub>)<sub>6</sub>]		monoclinic	C2/c	a=13.6775 b=11.51.34 11.2046 β=93.5909			cyclic
	Sm2[B<sub>2</sub>(SO<sub>4</sub>)<sub>6</sub>]		monoclinic	C2/c	a=13.633 b=11.492 c=11.112 β=93.567			cyclic
	Eu2[B<sub>2</sub>(SO<sub>4</sub>)<sub>6</sub>]		monoclinic	C2/c	a=13.602 b=11.470 c=11.050 β=93.465			cyclic
	Gd2[B<sub>2</sub>(SO<sub>4</sub>)<sub>6</sub>]		monoclinic	C2/c	a=13.5697 b=11.4426 c=11.0271 β=			cyclic
	Tb2[B<sub>2</sub>(SO<sub>4</sub>)<sub>6</sub>]		monoclinic	C2/c	a=13.5601 b=11.42.48 c=10.9881 β=93.534			cyclic
	Dy2[B<sub>2</sub>(SO<sub>4</sub>)<sub>6</sub>]		monoclinic	C2/c	a=13.568 b=11.425 c=10.9703 β=93.540			cyclic
	Ho2[B<sub>2</sub>(SO<sub>4</sub>)<sub>6</sub>]		monoclinic	C2/c	a=13.505 b=11.409 c=10.921 β=93.453			cyclic
	Er2[B<sub>2</sub>(SO<sub>4</sub>)<sub>6</sub>]		monoclinic	C2/c	a=13.551 b=11.411 c=10.882 β=93.41			cyclic
	Tm2[B<sub>2</sub>(SO<sub>4</sub>)<sub>6</sub>]		monoclinic	C2/c	a=13.4981 b=11.3617 10.8327 β=93.4500			cyclic
	Yb2[B<sub>2</sub>(SO<sub>4</sub>)<sub>6</sub>]		monoclinic	C2/c	a=13.495 b=11.3452 c=10.7961 β=93.390			cyclic
	Lu2[B<sub>2</sub>(SO<sub>4</sub>)<sub>6</sub>]		monoclinic	C2/c	a=13.469 b=11.364 c=10.799 β=93.369			cyclic
	Pb[B<sub>2</sub>(SO<sub>4</sub>)<sub>4</sub>]	613.05	orthorhombic	Pnna	a=12.516 b=12.521 c=7.302 Z=4	114.43	3.558	loop chain	^[26]
	Pb[B<sub>2</sub>O(SO<sub>4</sub>)<sub>3</sub>]		orthorhombic	P21/m	a=4.4000 b=12.1019 c=8.6043
	Bi2[B<sub>2</sub>(SO<sub>4</sub>)<sub>6</sub>]	659.08	orthorhombic	C2/c	a = 13.568, b = 11.490, c = 11.106 Z=4	1728.8	3.894
	(H3O)Bi[B(SO<sub>4</sub>)<sub>2</sub>]4	1039.72		I	a=11.857, c=8.149 Z=2	1156.84	2.99	colourless; non-linear optical
	(UO2)[B(SO<sub>4</sub>)<sub>2</sub>(SO<sub>3</sub>OH)]	569.52	triclinic	P	a=5.448 b=7.021 c=13.522 α =92.248° β =95.347° γ =101.987° Z=2		3.762	green	^[27]
	(UO2)2[B<sub>2</sub>O(SO<sub>4</sub>)<sub>3</sub>(SO<sub>3</sub>OH)<sub>2</sub>]	1058.23	monoclinic	P21/n	a=10.872 b=11.383 c=14.812 β=92.481 Z=4		3.838	yellow

Notes and References

1. Netzsch. Philip. Höppe. Henning A.. 2020-09-30. Synthesis and Characterization of the Chain Borosulfates (NH 4) 3 [B(SO 4) 3 ] and Sr[B 2 (SO 4) 4 ]. Zeitschrift für anorganische und allgemeine Chemie. en. 646. 18. 1563–1569. 10.1002/zaac.202000105. 0044-2313. free.
2. Schott . G. . Kibbel . H. U. . Über Sulfatoborate . Zeitschrift für anorganische und allgemeine Chemie . en . 314 . 1-2 . 104–112 . 10.1002/zaac.19623140113 . 0044-2313.
3. 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. Chinese Journal of Chemistry. en. 36. 1. 63–72. 10.1002/cjoc.201700597.
4. Logemann. Christian. Wickleder. Mathias S.. 2013-12-23. B 2 S 2 O 9 : A Boron Sulfate with Phyllosilicate Topology. Angewandte Chemie International Edition. en. 52. 52. 14229–14232. 10.1002/anie.201307056. 24214383.
5. Daub. Michael. Kazmierczak. Karolina. Höppe. Henning A.. Hillebrecht. Harald. 2013. The Borosulfate Story Goes on—From Alkali and Oxonium Salts to Polyacids. Chemistry – A European Journal. en. 19. 50. 16954–16962. 10.1002/chem.201303012. 24203813. 1521-3765.
6. Daub. Michael. Kazmierczak. Karolina. Gross. Peter. Höppe. Henning. Hillebrecht. Harald. 2013-05-20. Exploring a New Structure Family: Alkali Borosulfates Na 5 [B(SO 4) 4 ], A 3 [B(SO 4) 3 ] (A = K, Rb), Li[B(SO 4) 2 ], and Li[B(S 2 O 7) 2 ]]. Inorganic Chemistry. en. 52. 10. 6011–6020. 10.1021/ic400267s. 23656591. 0020-1669.
7. Bruns. Jörn. Höppe. Henning A.. Daub. Michael. Hillebrecht. Harald. Huppertz. Hubert. 2020-06-26. Borosulfates—Synthesis and Structural Chemistry of Silicate Analogue Compounds. Chemistry – A European Journal. en. 26. 36. 7966–7980. 10.1002/chem.201905449. 0947-6539. 7384169. 31943390.
8. Sutorius. Stefan. Hanrath. Michael. Bruns. Jörn. 2022-02-09. Be[B2(SO4)4] – A Borosulfate exhibiting Ino- and Phyllosilicate Analogue Topology. European Journal of Inorganic Chemistry. 2022 . 11 . en. ejic.202200009. 10.1002/ejic.202200009. 246719711. 1434-1948. free.
9. Ward. Matthew D.. Chaloux. Brian L.. Johannes. Michelle D.. Epshteyn. Albert. October 2020. Facile Proton Transport in Ammonium Borosulfate—An Unhumidified Solid Acid Polyelectrolyte for Intermediate Temperatures. Advanced Materials. en. 32. 42. 2003667. 10.1002/adma.202003667. 32924200. 221672277. 0935-9648. free. 2020AdM....3203667W .
10. 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]. Angewandte Chemie International Edition. 61. 4. en. anie.202112844. 10.1002/anie.202112844. 34626043. 238528455. 1433-7851.
11. Hämmer. Matthias. Bayarjargal. Lkhamsuren. Höppe. Henning A.. 2020-11-12. The First Bismuth Borosulfates Comprising Oxonium and a Tectosilicate-Analogous Anion. Angewandte Chemie International Edition. 60. 3. en. 1503–1506. 10.1002/anie.202011786. 7839778. 33026134. 1433-7851. free.
12. 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. Inorganic Chemistry. en. 57. 14. 8530–8539. 10.1021/acs.inorgchem.8b01234. 29957944. 0020-1669.
13. Netzsch. Philip. Pielnhofer. Florian. Glaum. Robert. Höppe. Henning A.. 2020-11-17. Synthesis-Controlled Polymorphism and Optical Properties of Phyllosilicate-Analogous Borosulfates M [B 2 (SO 4) 4 ] (M =Mg, Co). Chemistry – A European Journal. en. 26. 64. 14745–14753. 10.1002/chem.202003214. 7756226. 32744744. 0947-6539. free.
14. Li . Zijian . Jin . Wenqi . Zhang . Fangfang . Yang . Zhihua . Pan . Shilie . 2022-11-23 . Exploring Short-Wavelength Phase-Matching Nonlinear Optical Crystals by Employing KBe 2 BO 3 F 2 as the Template . ACS Central Science . en . 8 . 11 . 1557–1564 . 10.1021/acscentsci.2c00832 . 2374-7943 . 9686211 . 36439311.
15. Höppe. Henning A.. Kazmierczak. Karolina. Daub. Michael. Förg. Katharina. Fuchs. Franziska. Hillebrecht. Harald. 2012-06-18. The First Borosulfate K5[B(SO4)4]]. Angewandte Chemie International Edition. en. 51. 25. 6255–6257. 10.1002/anie.201109237. 22566359.
16. 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 . Inorganics . en . 7 . 12 . 145 . 10.3390/inorganics7120145 . 2304-6740. free .
17. Dong. Lingyun. Pan. Shilie. Wang. Ying. Yu. Hongwei. Lin. Xiaoxia. Han. Shujuan. March 2015. Synthesis and structural characterization of a new rubidium borosulfate, Rb5BS4O16. Materials Research Bulletin. en. 63. 93–98. 10.1016/j.materresbull.2014.11.047.
18. Daub . Michael . Hillebrecht . Harald . September 2015 . Borosulfates Cs 2 B 2 S 3 O 13, Rb 4 B 2 S 4 O 17, and A 3 HB 4 S 2 O 14 (A = Rb, Cs) – Crystalline Approximants for Vitreous B 2 O 3 ? . European Journal of Inorganic Chemistry . en . 2015 . 25 . 4176–4181 . 10.1002/ejic.201500603 . 1434-1948.
19. Li. Yanqiang. Zhou. Zhengyang. Zhao. Sangen. Liang. Fei. Ding. Qingran. Sun. Junliang. Lin. Zheshuai. Hong. Maochun. Luo. Junhua. 2021-03-08. A Deep-UV Nonlinear Optical Borosulfate with Incommensurate Modulations. Angewandte Chemie International Edition. 60. 20. en. 11457–11463. 10.1002/anie.202102107. 33686736. 232160602. 1433-7851.
20. Netzsch. Philip. Höppe. Henning A.. 2020-11-26. Sr[B 2 (SO 4) 3 (S 2 O 7)]

    A Borosulfate with an Unprecedented Chain Structure Comprising Disulfate Groups]

    . Inorganic Chemistry. 59. 24. en. 18102–18108. 10.1021/acs.inorgchem.0c02560. 33241934. 227175679. 0020-1669.
21. 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)]. Angewandte Chemie International Edition. 60. 36. en. 19740–19743. 34121302. 10.1002/anie.202106337 . 8456809 . 1433-7851. free.
22. Netzsch. Philip. Höppe. Henning A.. 2020-12-29. Ag[B(S2O7)2]: The First Transition Metal Borosulfate Featuring Disulfate Groups. European Journal of Inorganic Chemistry. 2021. 11. en. 1065–1070. 10.1002/ejic.202001095. 1434-1948. free.
23. Hämmer . Matthias . Höppe . Henning A. . 2022-09-02 . The Unconventional Cadmium Borosulfates Cd[B2O(SO4)3] and Cd4[B2O(SO4)6] . Zeitschrift für anorganische und allgemeine Chemie . 648 . 21 . en . zaac.202200197 . 10.1002/zaac.202200197 . 252059729 . 0044-2313. free .
24. van Gerven . David . Sutorius . Stefan . Bruns . Jörn . Wickleder . Mathias S. . 2022-07-20 . Stabilizing the Homopolycation (I 4) 2+ with a Hexasulfate in (I 4)[S 6 O 19 ] and a Borosulfate in (I 4)[B(S 2 O 7) 2 ] 2 . ChemistryOpen . 11 . 11 . e202200122 . en . 10.1002/open.202200122 . 35856862 . 9630045 . 250941699 . 2191-1363.
25. 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(S 2 O 7) 2 ] 2 as a Model System for the Structural Diversity in Borosulfate Chemistry]. Inorganic Chemistry. en. 59. 20. 15180–15188. 10.1021/acs.inorgchem.0c02156. 33001636. 222145994. 0020-1669.
26. Schönegger. Sandra. Bruns. Jörn. Gartner. Benjamin. Wurst. Klaus. Huppertz. Hubert. 2018-12-31. Synthesis and Characterization of the First Lead(II) Borosulfate Pb[B 2 (SO 4) 4 ]: Synthesis and Characterization of the First Lead(II) Borosulfate Pb[B 2 (SO 4) 4 ]. Zeitschrift für anorganische und allgemeine Chemie. en. 644. 24. 1702–1706. 10.1002/zaac.201800130. free.
27. 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 . Inorganic Chemistry . 61 . 40 . en . 15953–15960 . 10.1021/acs.inorgchem.2c02144 . 36047685 . 251977898 . 0020-1669.