The impact of the surrounding ligand field is successfully exploited in the case of Eu²⁺ to tune the emission characteristics of inorganic photoactive materials with potential application in, e.g., phosphor‐converted white light‐emitting diodes (pc‐wLEDs). However, the photoluminescence of Mn²⁺ related to intraconfigurational 3d⁵–3d⁵ transitions is also strongly dependent on local ligand field effects and has been underestimated in this regard so far. In this work, we want to revive the idea how to electronically tune the emission color of a transition metal ion in inorganic hosts by unusual electronic effects in the metal‐ligand bond. The concept is explicitly demonstrated for the weakly coordinating layer‐like borosulfate ligand in the Mn²⁺‐containing solid solutions Zn_1‐xMn_x[B₂(SO₄)₄] (x = 0, 0.03, 0.04, 0.05, 0.10). Zn[B₂(SO₄)₄]:Mn²⁺ shows orange narrow‐band luminescence at 590 nm, which is an unusually short wavelength for octahedrally coordinated Mn²⁺ and indicates an uncommonly weak ligand field. On the other hand, the analysis of the interelectronic Racah repulsion parameters reveals ionic Mn−O bonds with values close to the Racah parameters of the free Mn²⁺ ion. Overall, this strategy demonstrates that electronic control of the metal‐ligand bond can be a tool to make Mn²⁺ a potent alternative emitter to Eu²⁺ for inorganic phosphors.

Borosulfates are classified as silicate analogue materials. The number of crystallographically characterized compounds is still limited, whereas the structural diversity is already impressive. The anionic substructures of borosulfates exhibit vertex‐connected (BO₄)‐ and (SO₄)‐tetrahedra, whereas bridging between two (SO₄)‐ or even between two (BO₄)‐tetrahedra is scarce. The herein presented compound Sr[B₃O(SO₄)₄(SO₄H)] is the first borosulfate with a triple‐vertex linkage of three (BO₄) tetrahedra via one common oxygen atom. DFT calculations complement the experimental studies. Bader charges (calculated for all atoms) as well as charge‐density calculations give hint to the electron distribution within the anionic substructure and density‐of‐states calculations support the interpretation of the bonding situation.

Borosulfates are a rapidly expanding class of silicate analogue materials, where the structural diversity is expected to be at least as large as known for silicates. However, borosulfates with cross-linking of the anionic network into two or even three dimensions are still very rare. Herein, we present two new representatives with phyllosilicate analogue topology. Through solvothermal reactions of ZnO and MnCl₂∙4H₂O with boric acid in oleum (65% SO₃), we obtained single-crystals of Mn[B₂(SO₄)₄] (monoclinic, P2₁/n, Z = 2, a = 8.0435(4), b = 7.9174(4), c = 9.3082(4) Å, β = 110.94(1)°, V = 553.63(5) ų) and Zn[B₂(SO₄)₄] (monoclinic, P2₁/n, Z = 2, a = 7.8338(4), b = 8.0967(4), c = 9.0399(4) Å, β = 111.26(1)°, V = 534.36(5) ų). The crystal structures reveal layer-like anionic networks with alternating vierer- and zwölfer-rings formed exclusively by corner-linked (SO₄)- and (BO₄)-tetrahedra.

The phyllosilicate-analoguous borosulfate H ₂ [B ₂ (SO ₄ ) ₄ ] and its cadmium salt, Cd[B ₂ (SO ₄ ) ₄ ], have been synthesized via various paths and analyzed thoroughly. The heteropolyacid is the second structurally determined acid within borosulfate chemistry.

Five transition metal borates were synthesized in a Walker-type module under high-pressure/high-temperature conditions of 8–9 GPa and 800–1200 °C. They all exhibit the same interpenetrating, anionic borate network B ₁₂ O ₂₆ ¹⁶⁻ , crystallizing in the space group I 4 ₁ / acd , and therefore show high similarities to the borates Ti ₅ B ₁₂ O ₂₆ and Ga ₅ B ₁₂ O ₂₅ (OH). Cr ₅ B ₁₂ O ₂₅ (OH) and V ₅ B ₁₂ O ₂₅ (OH) are isotypic to Ga ₅ B ₁₂ O ₂₅ (OH), whereas Mn ₅ Mn _0.83 B ₁₂ O ₂₆ and Fe ₅ Fe _0.14 B ₁₂ O _24.3 (OH) _1.7 feature the partial occupation of an additional, cuboctahedral cavity in the structure. This is due to a partial reduction of the cations to the oxidation state +2, as presented with the novel compound Mn ₅ MnB ₁₂ O ₂₂ (OH) ₄ , which only features Mn ²⁺ for charge compensation. These structures feature a twelvefold coordination of manganese and iron.

Sulfur hexafluoride (SF ₆ ) is a persistent, highly potent greenhouse gas that is accumulating in the atmosphere at an increasing rate, exacerbating climate change. Whereas current degradation methods rely on forcing conditions to dissociate the inert molecule and additionally require post-treatment with basic solution to obtain harmless products, we show that SF ₆ is mineralized in a single step at ambient temperature using potassium hydroxide in water/isopropyl alcohol mixtures under UV irradiation. The reaction proceeds via an autocatalytic mechanism, where in situ-generated acetone acts as a photosensitizer, leading to the selective formation of potassium sulfite and fluoride salts. Compared to existing methods, this approach eliminates the need for extreme temperatures, hazardous catalysts, or post-treatment, providing a scalable and easy-to-apply strategy for SF ₆ degradation.