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  1. In this work, we report a dimeric cluster anion, {[CuGe 9 Mes] 2 } 4− , which was isolated as the [K(2,2,2-crypt)] + salt and characterized by using single-crystal X-ray diffraction and ESI mass spectroscopy. The title cluster represents the first locally σ-antiaromatic compound in the solid state, as well as the first heteroatomic antiaromatic compound. 
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  2. Abstract

    Antiaromaticity, as introduced in 1965, usually refers to monocyclic systems with 4nπ electrons. This concept was extended to all‐metal molecules after the observation of Li3Al4in the gas phase. However, the solid‐phase counterparts have not been documented to date. Herein, we describe a series of all‐metal antiaromatic anions, [Ln(η4‐Sb4)3]3−(Ln=La, Y, Ho, Er, Lu), which were isolated as the K([2.2.2]crypt) salts and identified by single‐crystal X‐ray diffraction. Based on the results obtained from the chemical bonding analysis, multicenter indices, and the electron‐counting rule, we conclude that the core [Ln(η4‐Sb4)3]3−fragment of the crystal has three locally π‐antiaromatic Sb4fragments. This complex represents the first locally π‐antiaromatic all‐metal system in the solid state, which is stabilized by interactions of the three π‐antiaromatic units with the central metal atom.

     
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