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Homoatomic polyanions of post‐transition main‐group metals, namely, Zintl anions, are precast in analogous Zintl phases and can react in solution to form new materials. Despite comprehensible reaction approaches, the formed products cannot be planned in advance, as hitherto undetected and therefore disregarded side reactions take place. The outcomes and interpretations of the reactions of Zintl anions...
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