Altering the spectroscopy, electronic structure, and bonding of organometallic curium(III) upon coordination of 4,4′−bipyridine
Brian N. Long, María J. Beltrán‐Leiva, Joseph M. Sperling, Todd N. Poe, Cristian Celis‐Barros, Thomas E. Albrecht‐Schmitt
Abstract
Abstract Structural and electronic characterization of (Cp′ 3 Cm) 2 ( μ −4,4′−bpy) (Cp′ = trimethylsilylcyclopentadienyl, 4,4′−bpy = 4,4′−bipyridine) is reported and provides a rare example of curium−carbon bonding. Cp′ 3 Cm displays unexpectedly low energy emission that is quenched upon coordination by 4,4′−bipyridine. Electronic structure calculations on Cp′ 3 Cm and (Cp′ 3 Cm) 2 ( μ −4,4′−bpy) rule out significant differences in the emissive state, rendering 4,4′−bipyridine as the primary quenching agent. Comparisons of (Cp′ 3 Cm) 2 ( 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.