Single crystals of [Au3Cl4][B(S2O7)2] and [Au2Cl4][B(S2O7)2](SO3) were obtained from a solvothermal reaction with SO3, and their electronic properties were investigated by means of density functional theory–based calculations. [Au3Cl4][B(S2O7)2] exhibits a cluster‐like cation, and the cationic gold–chloride strands in [Au2Cl4][B(S2O7)2](SO3) are found to resemble one‐dimensional metallic wires; this was further confirmed by polarization microscopy. More information can be found in the Research Article by B. Rasche, J. Bruns et al. (DOI: 10.1002/chem.202200004).

The reaction of elemental iodine and SO 3 in a sealed glass ampoule yielded a turquoise‐colored solution. At temperatures below 7 °C, deep red crystals of (I 4 )[S 6 O 19 ] grow. With the addition of B 2 O 3 and pyridine‐SO 3 complex red crystals of (I 4 )[B(S 2 O 7 ) 2 ] 2 can be obtained after heating the mixture to 120 °C. The combination of an (I 4 ) 2+ cation with oxoanions has previously not been observed. Both anions have a significant but different influence on the structural properties of the (I 4 ) 2+ cation.

(SO4)‐rich silicate analogue borosulfates are able to stabilise cationic cluster‐like and chain‐like aggregates. Single crystals of [Au3Cl4][B(S2O7)2] and [Au2Cl4][B(S2O7)2](SO3) were obtained by solvothermal reaction with SO3, and the electronic properties were investigated by means of density functional theory–based calculations. [Au3Cl4][B(S2O7)2] exhibits a cluster‐like cation, and the cationic gold‐chloride strands in [Au2Cl4][B(S2O7)2](SO3) are found to resemble one‐dimensional metallic wires. This is confirmed by polarisation microscopy.

Borosulfates are a constantly expanding class of silicate analogue compounds. The anionic substructures are composed of vertex‐connected (BO4)‐ and (SO4)‐tetrahedra and feature topologies of monomeric, oligomeric, and polymeric anions. The latter resemble typical motifs of ino‐, phyllo‐ and tectosilicates but none of the hitherto known borosulfates exhibits two different anion topologies within one structure. However, this is very rare even for the homopolyanionic silicates. Be[B2(SO4)4] is the first borosulfate featuring anionic chains and layers within one structure and both substructures are interconnected by (BeO4)‐tetrahedra. DFT calculations complement the experimental studies and help to describe the bonding situation of the Be−O bonds.