Highly Soluble Supertetrahedra upon Selective Partial Butylation of Chalcogenido Metalate Clusters in Ionic Liquids

Abstract

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.

Exploration of metal sulfide syntheses and the dissolution process of antimony sulfide in phosphonium-based ionic liquids

“…22,23,27–30 Among them, the most prominent compound contains the supersphere anion [Ge 24 Sn 36 Se 132 ]. 24–31,32 But also a new modification of K 2 Sn 2 S 5 was accessible, which obviously does not include the IL used. 33…”