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Ni[B 2 (SO 4 ) 4 ] and Co[B 2 (SO 4 ) 4 ]: Unveiling Systematic Trends in Phyllosilicate Analogue Borosulfates
Author(s) -
Pasqualini Leonard C.,
Janka Oliver,
Olthof Selina,
Huppertz Hubert,
Liedl Klaus R.,
Pöttgen Rainer,
Podewitz Maren,
Bruns Jörn
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202002221
Subject(s) - crystallography , x ray photoelectron spectroscopy , divalent , chemistry , crystal structure , tetrahedron , single crystal , x ray crystallography , diffraction , spectroscopy , physics , organic chemistry , nuclear magnetic resonance , quantum mechanics , optics
Borosulfates are compounds analogous to silicates, with heteropolyanionic subunits of vertex‐linked (SO 4 )‐ and (BO 4 )‐tetrahedra. In contrast to the immense structural diversity of silicates, the number of borosulfates is yet very limited and the extent of their properties is still unknown. This is particularly true for representatives with phyllosilicate and tectosilicate analogue anionic substructures. Herein, we present Ni[B 2 (SO 4 ) 4 ] and Co[B 2 (SO 4 ) 4 ], two new borosulfates with phyllosilicate analogue topology. While the anionic subunits of both structures are homeotypic, the positions of the charge compensating cations differ significantly: Ni II is located between the borosulfate layers, while Co II —in contrast—is embedded within the layer. Detailed analysis of these two structures based on single‐crystal X‐ray diffraction, magnetochemical investigations, X‐ray photoelectron spectroscopy, and quantum chemical calculations, unveiled the reasons for this finding. By in silico comparison with other divalent borosulfates, we uncovered systematic trends for phyllosilicate analogues leading to the prediction of new species.