Supertetrahedral clusters have been reported in two generally different types so far:one type possessing an organic ligand shell, no or lowc harges,a nd high solubility,w hile the other cluster type is ligand-free with usually high charges and low or no solubility in common solvents.T he latter is atremendous disadvantage regarding further use of the clusters in solution. However,a so rganic substituents usually broaden the HOMO-LUMO gaps,w hichc annot be overcompensated by the (limited) cluster sizes,afull organic shielding comes along with drawbacks regarding opto-electronic properties.We therefore sought to find aw ay of generating soluble clusters with am inimum number of organic substituents.H ere,w e present the synthesis and full characterization of two salts of [Sn 10 O 4 S 16 (SBu) 4 ] 4À that are high soluble in CH 2 Cl 2 or CH 3 CN, which includes first NMR and mass spectra obtained from solutions of such salts with mostly inorganic supertetrahedral clusters.The optical absorption properties of this new class of compounds indicates nearly unaffected band gaps.T he synthetic approach and the spectroscopic findings were rationalized and explained by means of high-level quantum chemical studies.
Studying structurally related families of compounds is a valuable tool in understanding and predicting material properties and has been extensively used for metal halide perovskites. Due to the variable anion structures in group 15 halogenido metalates, similar family relations are still largely missing. Herein, we present compounds featuring the [Sb2nI6n+4]4− family of anions, including the first n=5 member in [Hpyz]4[Sb10I34] (Hpyz=pyrazinium), which contains the largest halogenido pentelate anion reported to date. The optical properties of compounds featuring n=1–5 anions show a clear trend as well as an outlier, a low band gap of 1.72 eV for [Hpyz]4[Sb10I34], that can be well understood using quantum chemical investigations. Also using SbI3 and [H2NMe2]3[SbI6], a compound featuring a single octahedral [SbI6]3− unit, as limiting cases, we show that structure‐property relationships can be established in group 15 halogenido metalates in a similar way as in metal halide perovskites, thus providing a framework for understanding new and known compounds in this emerging class of materials.
Chalcogenides are one of the most versatile inorganic materials families, further subdivided into a large variety of specific groups of compounds, ranging from neat binary or multinary solids and nanoparticles...
Lead‐free heavy halogenido metalates are currently under intense investigation, as they show similarly promising semiconducting properties as their famous but toxic lead relatives. A major interest in this regard is the understanding and control of optical properties with the goal of designing highly efficient photoconducting materials. Here, we present two isostructural iodido pentelates (Hpyz)3E2I9 ⋅ 2H2O (pyz=pyrazine; E=Sb, Bi). Both compounds are stable up to 100 °C. We observe an inverted order of band gap sizes, 1.91 eV and 1.98 eV for the antimony and bismuth compound, respectively, compared to similar pairs of compounds. We use DFT calculations to confirm that this surprising finding can be traced back to the presence of charge transfer excitations in both compounds.
Supertetrahedral clusters have been reported in two generally different types so far:one type possessing an organic ligand shell, no or lowc harges,a nd high solubility,w hile the other cluster type is ligand-free with usually high charges and low or no solubility in common solvents.T he latter is atremendous disadvantage regarding further use of the clusters in solution. However,a so rganic substituents usually broaden the HOMO-LUMO gaps,w hichc annot be overcompensated by the (limited) cluster sizes,afull organic shielding comes along with drawbacks regarding opto-electronic properties.We therefore sought to find aw ay of generating soluble clusters with am inimum number of organic substituents.H ere,w e present the synthesis and full characterization of two salts of [Sn 10 O 4 S 16 (SBu) 4 ] 4À that are high soluble in CH 2 Cl 2 or CH 3 CN, which includes first NMR and mass spectra obtained from solutions of such salts with mostly inorganic supertetrahedral clusters.The optical absorption properties of this new class of compounds indicates nearly unaffected band gaps.T he synthetic approach and the spectroscopic findings were rationalized and explained by means of high-level quantum chemical studies.
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