[Hg₄Te₈(Te₂)₄]⁸⁻: A Heavy Metal Porphyrinoid Embedded in a Lamellar Structure

Abstract

The use of ionic liquids (C C Im)[BF ] with long alkyl chains (n=10, 12) in the ionothermal treatment of Na [HgTe ] led to lamellar crystal structures with molecular macrocyclic anions [Hg Te ] (1), the heaviest known topological relative of porphyrin. [Hg Te ] differs from porphyrin by the absence of an electronic π-system, which prevents a "global" aromaticity. Quantum chemical studies reveal instead small ring currents in the pyrrole-type five-membered rings that indicate weak local (σ) aromaticity. As a result of their lamellar nature, the compounds are promising candidates for the formation of sheets containing chalcogenidometalate anions.

Stabilizing a metalloid {Zn12} unit within a polymetallide environment in [K2Zn20Bi16]6−

“…Calculations of [Hg 8 Te 16 ] 8− were performed with the same settings as above, but employed the same basis set as in ref. 39 .…”

“…The high flexibility of purely inorganic mimics of porphine was recently shown on the example of [Hg 8 Te 16 ] 8− (ref. 39 ). However, while the latter possesses 120 valence electrons, hence more valence electrons than porphine, the electron count in {Zn 8 Bi 16 } q− is lower than that in the organic macrocycle.…”

“…It is not a direct measure of aromaticity 44 . Furthermore, the nucleus-independent chemical shift (NICS) approach 48 39 , and an insignificant NICS value of 1.3 and 1.2 ppm, respectively. Figure 3 illustrates the calculated electrostatic potential with and without coordination of K + .…”

Ionic liquid cations as methylation agent for extremely weak chalcogenido metalate nucleophiles

“…As the third system to be studied, the salt of a polymeric tellurido mercurate anion, Na 2 [HgTe 2 ],35 was treated with ionic liquids comprising hexyl or octyl chains. Recently, we reported about very uncommon tellurido mercurate anions [Hg 8 Te 16 ] 8– to be stabilized by imidazolium salts with decyl or dodecyl chains,36 so we were eager to probe the effect of counterions with medium-size alkyl chain lengths. Indeed, molecular cluster anions were received again, yet with another cluster structure and methylated terminal Te ligands.…”

Formation of [(CnC1imTe)4Hg]2+ (n = 6, 8) upon in‐situ Generation of Dialkylimidazole‐2‐Tellurones in Ionic Liquids at Room Temperature

“…Under inert conditions, alkali metal salts of tellurido mercurates exhibit good solubility in imidazolium‐based ionic liquids at room temperature, and undergo the following types of reactions at slightly elevated temperatures of 60–80 °C: (a) rearrangement reactions, leading to tellurido mercurate substructures of different dimensionalities within the resulting imidazolium salts; the dimensionality can be controlled by variation of the alkyl chain lengths of the ionic liquid cation , . (b) partial oxidation of some of the telluride ligands with formation of ditelluride units.…”