Heavy Chalcogenide-Based Ionic Liquids in Syntheses of Metal Chalcogenide Materials near Room Temperature

室温附近金属硫族化合物材料合成中的重硫族化物基离子液体

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Abstract

This minireview describes two strategically different and unexplored approaches to use ionic liquids (IL) containing weakly solvated and highly reactive chalcogenide anions [E-SiMe(3) ](-) and [E-H](-) of the heavy chalcogens (E=S, Se, Te) in materials synthesis near room temperature. The first strategy involves the synthesis of unprecedented trimethylsilyl chalcogenido metalates Cat(+) [M(E-SiMe(3) )(n) ](-) (Cat=organic IL cation) of main group and transition metals (M=Ga, In, Sn, Zn, Cu, Ag, Au). These fully characterized homoleptic metalates serve as thermally metastable precursors in low-temperature syntheses of binary, ternary and even quaternary chalcogenide materials such as CIGS and CZTS relevant for semiconductor and photovoltaics (PV) applications. Furthermore, thermally and protolytically metastable coinage metalates Cat(+) [M(ESiMe(3) )(2) ](-) (M=Cu, Ag, Au; E=S, Se) are accessible. Finally, the use of precursors BMPyr[E-SiMe(3) ] (E=Se,Te; BMPyr=1-butyl-1-methylpyrrolidinium) as sources of activated selenium and tellurium in the synthesis of high-grade thermoelectric nanoparticles Bi(2) Se(3) and Bi(2) Te(3) is shortly highlighted. The second synthesis strategy involves the metalation of ionic liquids Cat[S-H] and Cat[Se-H] by protolytically highly active metal alkyls or amides R(n) M. This rather general approach towards unknown chalcogenido metalates Cat(m) [R(n-1) M(E)](m) (E=S, Se) will be demonstrated in a research paper following this short review head-to-tail.

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