Altering the spectroscopy, electronic structure, and bonding of organometallic curium(III) upon coordination of 4,4'-bipyridine.

Long, Brian N; Beltrán-Leíva, María J; Sperling, Joseph M; Poe, Todd N; Celis-Barros, Cristian; Albrecht-Schönzart, Thomas E · Nat Commun · 2023

basic_science · Level V

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Abstract

Structural and electronic characterization of (Cp'<sub>3</sub>Cm)<sub>2</sub>(μ-4,4'-bpy) (Cp' = trimethylsilylcyclopentadienyl, 4,4'-bpy = 4,4'-bipyridine) is reported and provides a rare example of curium-carbon bonding. Cp'<sub>3</sub>Cm displays unexpectedly low energy emission that is quenched upon coordination by 4,4'-bipyridine. Electronic structure calculations on Cp'<sub>3</sub>Cm and (Cp'<sub>3</sub>Cm)<sub>2</sub>(μ-4,4'-bpy) rule out significant differences in the emissive state, rendering 4,4'-bipyridine as the primary quenching agent. Comparisons of (Cp'<sub>3</sub>Cm)<sub>2</sub>(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.

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