Ma Jun, Chen Teng-Teng, Li Honglin, Bumüller Dennis, Weigend Florian, Jian Tian, Kappes Manfred M, Schooss Detlef, Li Wan-Lu, Xing Xiao-Peng, Wang Lai-Sheng
Shanghai Key Lab of Chemical Assessment and Sustainability and Department of Chemistry, Tongji University, 1239 Siping Road, Shanghai 200092, China.
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon 999077, Hong Kong (SAR), China.
Sci Adv. 2024 Nov;10(44):eads4724. doi: 10.1126/sciadv.ads4724. Epub 2024 Oct 30.
The reactivity of Bi clusters ( = 2 to 30) with O is found to display even-odd alternations. The open-shell even-sized Bi clusters are more reactive than the closed-shell odd-sized clusters, except Bi, which exhibits no observable reactivity toward O. We have investigated the structure and bonding of Bi to understand its remarkable resistance to oxidation. We find that the most stable structure of Bi consists of two Bi cages linked by a Bi dimer, where each atom is bonded to three neighboring atoms. Chemical bonding analyses reveal that each Bi uses its three 6 electrons to form three covalent bonds with its neighbors, resulting in a Bi cluster without any dangling bonds. We find that the robust Bi framework along with the totally delocalized unpaired electron is responsible for the surprising inertness of Bi toward O. The Bi framework is similar to that in Hittorf's phosphorus, suggesting the possibility to create bismuth nanoclusters with interesting structures and properties.
已发现铋团簇（(n = 2)至(30)）与氧的反应性呈现奇偶交替。除了铋对氧没有可观察到的反应性外，开壳层偶数尺寸的铋团簇比闭壳层奇数尺寸的团簇更具反应性。我们研究了铋的结构和键合，以了解其对氧化的显著抗性。我们发现铋最稳定的结构由两个通过铋二聚体连接的铋笼组成，其中每个原子与三个相邻原子键合。化学键分析表明，每个铋利用其三个(6p)电子与相邻原子形成三个共价键，从而形成一个没有任何悬空键的铋团簇。我们发现，坚固的铋框架以及完全离域的未配对电子是铋对氧具有惊人惰性的原因。铋框架与希托夫磷中的框架相似，这表明有可能创造出具有有趣结构和性质的铋纳米团簇。
