Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, Tallahassee, FL, 32306, USA.
Department of Chemistry and Nuclear Science & Engineering Center, Colorado School of Mines, Golden, CO, 80401, USA.
Nat Commun. 2023 Jun 24;14(1):3774. doi: 10.1038/s41467-023-39481-7.
Structural and electronic characterization of (Cp'Cm)(μ-4,4'-bpy) (Cp' = trimethylsilylcyclopentadienyl, 4,4'-bpy = 4,4'-bipyridine) is reported and provides a rare example of curium-carbon bonding. Cp'Cm displays unexpectedly low energy emission that is quenched upon coordination by 4,4'-bipyridine. Electronic structure calculations on Cp'Cm and (Cp'Cm)(μ-4,4'-bpy) rule out significant differences in the emissive state, rendering 4,4'-bipyridine as the primary quenching agent. Comparisons of (Cp'Cm)(μ-4,4'-bpy) with its samarium and gadolinium analogues reveal atypical bonding patterns and electronic features that offer insights into bonding between carbon with f-block metal ions. Here we show the structural characterization of a curium-carbon bond, in addition to the unique electronic properties never before observed in a curium compound.
报告了 (Cp'Cm)(μ-4,4'-bpy)（Cp'=三甲基甲硅烷基环戊二烯基，4,4'-bpy=4,4'-联吡啶）的结构和电子特性，为钚-碳键提供了一个罕见的例子。Cp'Cm 表现出出人意料的低能量发射，而配位 4,4'-联吡啶后则被猝灭。对 Cp'Cm 和 (Cp'Cm)(μ-4,4'-bpy) 的电子结构计算排除了发射态的显著差异，使 4,4'-联吡啶成为主要猝灭剂。(Cp'Cm)(μ-4,4'-bpy)与其钐和钆类似物的比较揭示了典型的键合模式和电子特征，为碳与 f 区金属离子之间的键合提供了深入了解。在这里，我们展示了一个钚-碳键的结构特征，以及在钚化合物中从未观察到的独特电子性质。
