A Facile Route for the Synthesis of Polycationic Tellurium Cluster Compounds: Synthesis in Ionic Liquid Media and Characterization by Single‐Crystal X‐ray Crystallography and Magnetic Susceptibility

Abstract

Abstract. An innovative soft chemical approach has been applied, using ionic liquids as an alternative reaction medium for the synthesis of tellurium polycationic cluster compounds at room temperature. [

Controlled Synthesis of Polyions of Heavy Main-Group Elements in Ionic Liquids

“…In addition, the concentration of the different halogenidometalate species can be tuned by temperature [100], mole fraction of employed MX 3 [5], and by adding additional free X − anions [5100]. The latter has been utilized by Ruck et al to overcome hindered crystallization of products by adding small amounts of NaCl after completion of the reaction to increase the mole fraction of [AlCl 4 ] − [23,26,101]. …”

“…A variety of homoatomic polycations of group 15 or 16 elements has been synthesized in ILs [26,27,31,99,101,102,103,104] and several influencing reaction parameters were deduced.…”

“…Apart from Te 4 2+ , which proves a dominance in Lewis-acidic AlCl 3 -containing ILs similar to Bi 5 3+ , several other tellurium polycations (Figure 5) were accessed in ILs [26,27,31,101,102,103]. Thereby, the utilization of an IL as reaction medium can lead to extraordinary properties of the reaction product as the following example demonstrates: Te 4 [Bi 0.67 Cl 4 ] obtained from a gas-phase transport reaction is an conventional semiconductor.…”

“…Omitting any bismuth-containing starting materials leads to the formation of pure Te 4 [AlCl 4 ] 2 under the same conditions [101]. Te 4 [Al 2 Cl 7 ] 2 has been synthesized during an attempt to access phosphorus-tellurium polycations by reacting equimolar amounts of tellurium, TeI 4 , and red phosphorus in the same IL with n = 4.8 at 80 °C [26].…”

“…Ahmed et al obtained pure Te 6 [WOCl 4 ] 2 by oxidizing elemental tellurium using WOCl 4 under otherwise identical conditions compared to the formation of Te 4 [AlCl 4 ] 2 [101]. Similarly, Feldmann et al obtained [Te 8 ] 2 [Ta 4 O 4 Cl 16 ] by reacting elemental tellurium, TeCl 4 , TaOCl 3 , and TaCl 5 in the molar ratio of 7:1:2:1 in [BMIm]Cl [103].…”