Borosulfate

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	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	[7]
	H[B(HSO4)4]		monoclinic	P21/c	a=15.6974, b=11.436, c=8.5557; β=90.334°; Z=8			superacid	[8] [9]
	H3O[B(SO4)2]			P4/ncc	a=9.1377, c=7.3423; Z=4				[9]
	H[B(SO4)(S2O7)]		monoclinic	P21/c	a=15.697 b=11.4362 c=8.5557 β=90.334				[4]
	Li[B(SO4)2]			Pc	a = 7.635, b = 9.342, c = 8.432, and β = 92.55°			3D network, like tectosilicate	[8] [10]
	Li[B(S2O7)2]		orthorhombic	P212121	a = 10.862, b = 10.877, c = 17.769				[8] [10]
	Li5[B(SO4)4]		orthorhombic	P21/c	a=8.0191 b=10.2111 c=15.0401				[4]
	Be[B2(SO4)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]
	NH4[B(SO4)2]			P4/ncc	a=9.1980 c=7.2458			decompose 320 °C, proton conductor	[4] [12]
	NH4[B(S2O7)2]		monoclinic	Cc	a=11.4403 b=14.9439 c=13.8693 β=93.662				[8] [4]
	(NH4)2B4SO10	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	[13]
	(NH4)3H2[BOB(PO4)3]		monoclinic	P21/c	a=7.7506 b=6.6685 c=24.355 β=92.562° Z=4	1257.5	2.000	white	[14]
	[NH4]3[B(SO4)3]	343.12	orthorhombic	Ibca	a=7.2858 b=14.7048 c=22.7052 Z=8	2433.2	1.928	decompose 320 °C chains	[15] [2]
	Na[B(SO4)2]		monoclinic	P2/c	a=5.434 b=7.570 c=7.766 β=99.74				[4]
	Na[B(S2O7)2]		monoclinic	P21/c	a=10.949, b=8.49, c=12.701; β=110.227°; Z=4				[8] [9]
	Na2B6SO13		orthorhombic	Pbca	a=11.6569 b=9.4094 c=17.4833 Z=8	1917.6	2.431	birefringence Δn = 0.07 @ 589.3 nm	[16]
	Na5[B(SO4)4]-I		orthorhombic	Pca21	a = 10.730, b = 13.891, c = 18.197				[10]
	Na5[B(SO4)4]-II		orthorhombic	P212121	a = 8.624, b = 9.275, c = 16.671				[10]
	Na5[BOB(PO4)3]							white	[14]
	α-Mg4[B2O(SO4)6]	711.22	trigonal	P3	a=8.0165 c=7.4858 Z=1	416.62	2.835	colourless	[6]
	β-Mg4[B2O(SO4)6]	711.22	hexagonal	P3	a = 13.9196, c = 7.4854, Z = 3	1253	2.821	colourless	[6]
	Mg[B2(SO4)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 decompose 550 °C	[6]
	β-Mg[B2(SO4)4]		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	[17]
	Mg3((H2O)B(SO4)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	[16]
	Mg3((H2O)B(SO4)3)2	706.94		R3	a=7.9620 c=24.4231 Z=3	1340.84	2.627	room temperature	[16]
	K[B(SO4)2]			P4/ncc	a=8.9739 c=7.4114				[4]
	K[B(S2O7)2]		monoclinic	Cc	a=11.3368, b=14.66, c=13.6650; β=94.235°; Z=8				[8] [9]
	K2B4SO10	313.50	monoclinic	C2	a=11.2631 b=6.4339 c=12.649 β=105.707° Z=4	882.4	2.360	colourless	[18]
pentapotassium borosulfate	K5[B(SO4)4]			P41	a=9.9023 c=16.1871	1687.2	2.471	first discovered	[8] [1]
	K3[B(SO4)3]		orthorhombic	Ibca	a = 7.074, b = 14.266, c = 22.58				[8] [10]
	K4[BS4O15(OH)]		monoclinic	I2/a	a=14.524 b=7.3916 c=15.7857 β=115.50				[4]
	CaB2S4O16		monoclinic	P21/c	a=5.5188 b=15.1288 c=13.2660 β=92.88			sheet	[4]
	Mn[B2(SO4)4]		monoclinic	P21/n	a = 8.0435, b = 7.9174, c = 9.3082, β = 110.94° Z=2	553.63		colourless	[19]
	α-Mn4[B2O(SO4)6]	833.74	trigonal	P3	a=8.1086 c=7.7509 Z=1	441.3	3.137	colourless	[6]
	β-Mn4[B2O(SO4)6]	833.74	trigonal	P3	a=13.9196 c=7.4854
	α-Co[B2(SO4)4]		monoclinic	C2/c	a=17.4254 b=5.3397 c=14.3214 β=126.03° Z=4	269.40	2.860	pink	[17]
	β-Co[B2(SO4)4]		monoclinic	P21/n	a=7.8892 b=8.1042 c= 9.0409 β=111.29° Z=2	269.29	2.803	pink	[17]
	α-Co4[B2O(SO4)6]	849.70	trigonal	P3	a=7.991 c=7.669 Z=1	418.0	3.376	pink	[6]
	α-Ni4[B2O(SO4)6]	848.82	trigonal	P3	a=7.9359 c=7.4398 Z=1	405.77	3.474	yellow	[6]
	Cu[B(SO4)2(HSO4)]		triclinic	P1	a=5.3096 b=7.0752 c=11.1977 α=81.154 β=80.302 γ=80.897			cyclic	[4]
	Cu[B2(SO4)4]		triclinic	P1	a=5.2470 b=7.1371 c=7.9222 α=73.814 β=70.692 γ=86.642			chain	[4]
	Zn[B2(SO4)4]		monoclinic	P21/n	a = 8.0435, b = 7.9174, c = 9.3082, β = 111.26° Z=2	534.36		colourless	[19]
	α-Zn4[B2O(SO4)6]	875.46	trigonal	P3	a=7.9971 c=7.4895 Z=1	414.81	3.505	colourless	[6]
	Rb2B4SO10	406.24	monoclinic	C2	a=11.3127 b=6.5152 c=12.971 β=105.411° Z=4	921.6	2.928	colourless	[18]
	Rb3[B(SO4)3]		orthorhombic	Ibca	a = 7.2759, b = 14.794, c = 22.637				[10]
	Rb4[B2O(SO4)4]		orthorhombic	Pnma	a=8.0415 b=10.647 c=20.425				[4]
	Rb5[B(SO4)4]		tetragonal	P43212	a=10.148 c=16.689 Z=4			band gap 3.99 eV	[4] [20]
	Rb3HB4S2O14			P63/m	a = 6.502, c = 19.02 Z=2				[21]
	Rb3H2[BOB(PO4)3]							white	[14]
	LiRb4[B(SO4)4]	743.8	monoclinic	P21	a=7.5551, c=14.560, c=7.5517 β=90.2372 Z=2			transparent	[22]
	LiRb4[B(SO4)4]	743.8	tetragonal	I4	a=7.6128, c=14.631, Z=2			at 500K	[22]
	Sr[B2(SO4)4]	493.48	orthorhombic	Pnma	a=12.574 b=12.421 c=7.319 Z=4	1143.1	2.867	decompose 400 °C	[8] [2]
	Sr[B2(SO4)3(S2O7)]	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[B2O(SO4)3]		orthorhombic	Pnma	a=1657.3 b=12.037 c=4.39484				[8] [4]
	Sr[B3O(SO4)4(SO4H)]	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	[23]
	Y2[B2(SO4)6]		monoclinic	C2/c	a=13.5172 b=11.3941 c=10.8994 β=93.447			cyclic	[15] [4]
	Pd[B(S2O7)2]2		monoclinic	P21/c	a = 7.2686 b = 12.7802 c = 11.4930 β = 101.343° Z=2	1046.8	2.64	blue	[24]
	Pd[B(S2O7)2]2		tetragonal	P41	a = 13.8210 c = 21.724 Z=8	4149.7	2.66	blue	[24]
	Pd[B(SO4)(S2O7)]2		monoclinic	P21/c	a = 6.7061 b = 16.0198 c = 8.1681 β = 94.923° Z = 2	874.27	2.55	red	[24]
	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	[25]
	Cd[B2(SO4)4]								[26]
	Cd[B2O(SO4)3]	438.20	orthorhombic	Pnma	a=8.9692 b=11.520 c=8.7275 Z=4	901.8	3.23	colourless	[26]
	Cd4[B2O(SO4)6]		trigonal	P3	a=8.2222 c=7.9788 Z=1	467.14	3.78	colourless	[26]
	(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	[27]
	Cs2B4SO10	501.12	monoclinic	C2	a=11.4012 b=6.5997 c=13.5702 β=103.934° Z=4	919.04	3.359	colourless	[18]
	Cs2[B2O(SO4)3]		monoclinic	P2/c	a=14.765 b=6.710 c=12.528 β=104.50				[21]
	Cs3HB4S2O14			P63/m	a = 6.5648, c = 19.5669 Z=2				[21]
	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	[14]
	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				[15] [4]
	Cs3Na2[B(SO4)4]		monoclinic	P21/c	a=13.6406 b=7.9475 c=13.9573 β=990.781				[15] [4]
	CsK4[B(SO4)4]			P43212	a=9.9433 c=16.881				[15] [4]
	Ba[B2(SO4)4]		orthorhombic	Pnna	a = 12.791, b = 12.800, c = 7.317 Z = 4				[8] [28]
	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] [28]
	La2[B2(SO4)6]		monoclinic	C2/c	a=1379.2 b=1158.9 c=1139.5 β=93.611			cyclic	[15] [4]
	Ce2[B2(SO4)6]		monoclinic	C2/c	13.740 b=11.5371 c=11.3057 β=93.661			cyclic	[15] [4]
	Pr2[B2(SO4)6]		monoclinic	C2/c	a=13.711 b=11.5305 c=11.2643 β=93.668			cyclic	[15] [4]
	Nd2[B2(SO4)6]		monoclinic	C2/c	a=13.6775 b=11.51.34 11.2046 β=93.5909			cyclic	[15] [4]
	Sm2[B2(SO4)6]		monoclinic	C2/c	a=13.633 b=11.492 c=11.112 β=93.567			cyclic	[15] [4]
	Eu2[B2(SO4)6]		monoclinic	C2/c	a=13.602 b=11.470 c=11.050 β=93.465			cyclic	[15] [4]
	Gd2[B2(SO4)6]		monoclinic	C2/c	a=13.5697 b=11.4426 c=11.0271 β=			cyclic	[15] [4]
	Tb2[B2(SO4)6]		monoclinic	C2/c	a=13.5601 b=11.42.48 c=10.9881 β=93.534			cyclic	[15] [4]
	Dy2[B2(SO4)6]		monoclinic	C2/c	a=13.568 b=11.425 c=10.9703 β=93.540			cyclic	[15] [4]
	Ho2[B2(SO4)6]		monoclinic	C2/c	a=13.505 b=11.409 c=10.921 β=93.453			cyclic	[15] [4]
	Er2[B2(SO4)6]		monoclinic	C2/c	a=13.551 b=11.411 c=10.882 β=93.41			cyclic	[15] [4]
	Tm2[B2(SO4)6]		monoclinic	C2/c	a=13.4981 b=11.3617 10.8327 β=93.4500			cyclic	[15] [4]
	Yb2[B2(SO4)6]		monoclinic	C2/c	a=13.495 b=11.3452 c=10.7961 β=93.390			cyclic	[15] [4]
	Lu2[B2(SO4)6]		monoclinic	C2/c	a=13.469 b=11.364 c=10.799 β=93.369			cyclic	[15] [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	[24] [29]
	[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	[24] [29]
	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] [30]
	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		[15]
	(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	[15]
	(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	[31]
	(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	[31]

References

1. 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. 51 (25): 6255–6257. Bibcode:2012ACIE...51.6255H. doi:10.1002/anie.201109237. PMID   22566359.
2. 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. 646 (18): 1563–1569. Bibcode:2020ZAACh.646.1563N. doi: 10.1002/zaac.202000105 . ISSN   0044-2313.
3. Schott, G.; Kibbel, H. U. (1962). "Über Sulfatoborate" . Zeitschrift für anorganische und allgemeine Chemie. 314 (1–2): 104–112. Bibcode:1962ZAACh.314..104S. doi:10.1002/zaac.19623140113. ISSN   0044-2313.
4. 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. 26 (36): 7966–7980. Bibcode:2020ChEuJ..26.7966B. doi:10.1002/chem.201905449. ISSN   0947-6539. PMC   7384169 . PMID   31943390.
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". Chinese Journal of Chemistry. 36 (1): 63–72. doi:10.1002/cjoc.201700597.
6. 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. 57 (14): 8530–8539. doi:10.1021/acs.inorgchem.8b01234. ISSN   0020-1669. PMID   29957944.
7. Logemann, Christian; Wickleder, Mathias S. (2013-12-23). "B 2 S 2 O 9 : A Boron Sulfate with Phyllosilicate Topology". Angewandte Chemie International Edition. 52 (52): 14229–14232. Bibcode:2013ACIE...5214229L. doi:10.1002/anie.201307056. PMID   24214383.
8. 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): 18102–18108. doi:10.1021/acs.inorgchem.0c02560. ISSN   0020-1669. PMID   33241934. S2CID   227175679.
9. 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. 19 (50): 16954–16962. Bibcode:2013ChEuJ..1916954D. doi:10.1002/chem.201303012. ISSN   1521-3765. PMID   24203813.
10. 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. 52 (10): 6011–6020. doi:10.1021/ic400267s. ISSN   0020-1669. PMID   23656591.
11. 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): ejic.202200009. Bibcode:2022EJIC.2022E0009S. doi: 10.1002/ejic.202200009 . ISSN   1434-1948. S2CID   246719711.
12. 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. 32 (42): 2003667. Bibcode:2020AdM....3203667W. doi: 10.1002/adma.202003667 . ISSN   0935-9648. PMID   32924200. S2CID   221672277.
13. 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): anie.202112844. doi:10.1002/anie.202112844. ISSN   1433-7851. PMID   34626043. S2CID   238528455.
14. Ridenour, J. August; Chaloux, Brian L.; Johannes, Michelle D.; Bernstein, Noam; Finn, Matthew T.; Ryou, Heonjune; Epshteyn, Albert (2025-08-01). "Cs 3 H 2 [BOB(PO 4 ) 3 ] - the Best-Performing 1D Borophosphate Intermediate Temperature Proton Electrolyte". ACS Omega acsomega.5c04320. doi:10.1021/acsomega.5c04320. ISSN   2470-1343.
15. 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): 1503–1506. doi: 10.1002/anie.202011786 . ISSN   1433-7851. PMC   7839778 . PMID   33026134.
16. 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" . Science China Chemistry. 68 (2): 475–480. doi:10.1007/s11426-024-2170-6. ISSN   1674-7291.
17. 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. 26 (64): 14745–14753. doi: 10.1002/chem.202003214 . ISSN   0947-6539. PMC   7756226 . PMID   32744744.
18. 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. 8 (11): 1557–1564. doi:10.1021/acscentsci.2c00832. ISSN   2374-7943. PMC   9686211 . PMID   36439311.
19. 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. 7 (12): 145. doi: 10.3390/inorganics7120145 . ISSN   2304-6740.
20. 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. 63: 93–98. doi:10.1016/j.materresbull.2014.11.047.
21. 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. 2015 (25): 4176–4181. Bibcode:2015EJIC.2015.4176D. doi:10.1002/ejic.201500603. ISSN   1434-1948.
22. 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): 11457–11463. Bibcode:2021ACIE...6011457L. doi:10.1002/anie.202102107. ISSN   1433-7851. PMID   33686736. S2CID   232160602.
23. 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): 19740–19743. doi: 10.1002/anie.202106337 . ISSN   1433-7851. PMC   8456809 . PMID   34121302.
24. Sutorius, Stefan; Patrun, David; Edelmann, Arthur; Schumacher, Lars; Pöttgen, Rainer; Suta, Markus; Bruns, Jörn (2025-07-25). "Pd[B(S 2 O 7 ) 2 ] 2 and Pd[B(SO 4 ) (S 2 O 7 )] 2 : Two Borosulfates with Pd 2+ in Octahedral and One with Pd 2+ in Square Planar Oxygen Coordination". Chemistry – A European Journal. 31 (42) e202501515. doi:10.1002/chem.202501515. ISSN   0947-6539. PMID   40454746.
25. 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): 1065–1070. doi: 10.1002/ejic.202001095 . ISSN   1434-1948.
26. 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): zaac.202200197. Bibcode:2022ZAACh.648E0197H. doi: 10.1002/zaac.202200197 . ISSN   0044-2313. S2CID   252059729.
27. 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. doi:10.1002/open.202200122. ISSN   2191-1363. PMC   9630045 . PMID   35856862. S2CID   250941699.
28. 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. 59 (20): 15180–15188. doi:10.1021/acs.inorgchem.0c02156. ISSN   0020-1669. PMID   33001636. S2CID   222145994.
29. Sutorius, Stefan; van Gerven, David; Olthof, Selina; Rasche, Bertold; Bruns, Jörn (2022-04-19). "Polycations Stabilised by Borosulfates: [Au 3 Cl 4 ][B(S 2 O 7 ) 2 ] and the One-Dimensional Metal [Au 2 Cl 4 ][B(S 2 O 7 ) 2 ](SO 3 )". Chemistry – A European Journal. 28 (22) e202200004. Bibcode:2022ChEuJ..28E0004S. doi:10.1002/chem.202200004. ISSN   0947-6539. PMC   9314955 . PMID   35262987.
30. 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. 644 (24): 1702–1706. doi: 10.1002/zaac.201800130 .
31. 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): 15953–15960. doi:10.1021/acs.inorgchem.2c02144. ISSN   0020-1669. PMID   36047685. S2CID   251977898.