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Abstract:
Three new pnicogen-chalcogen polycations were synthesized under specific
conditions in the Lewis-acidic ionic liquids (ILs) [EMIm]XnAlX(3) and
[BMIm]XnAlX(3) (X = Cl, Br; [EMIm]: 1-ethyl-3-methylimidazolium, [BMIm]:
1-butyl-3-methylimidazolium) and crystallized as their
tetrahalogenidoaluminate salts. Single-crystal X-ray diffraction
revealed the new polycation [Bi6Te4Br2](4+) in triclinic
[Bi6Te4Br2](AlBr4)(4) as the reaction product of bismuth, tellurium, and
bismuth tribromide. Substitution of the elements with Bi2Te3 yielded the
heterocubane [Bi4Te4](4+) in tetragonal [Bi4Te4](AlBr4)(4), which
crystallizes isotypically to its known chlorine counterpart. The latter
is also accessible from ILs. The interactions between cations and anions
were evaluated by quantum-chemical calculations. Bi2S3, which is
insoluble in most media, readily dissolves in the employed IL and forms
the new augmented heterocubane [Bi3S4AlCl](3+), which crystallizes with
the complex anion [S(AlCl3)(3)](2-) as triclinic
[Bi3S4AlCl][S(AlCl3)(3)]AlCl4. Quantum-chemical calculations support the
assignment of elements in this compound. The monoclinic crystal
structure of [Sb13Se16](AlCl4)(6)(Al2Cl7) contains a new member of the
small family of pnicogen-chalcogen spiro-heterocubanes.
