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Updated: Jul 10, 2026

A Novel Technique for Raman Analysis of Highly Radioactive Samples Using Any Standard Micro-Raman Spectrometer
Published on: April 12, 2017
Highly oxidizing excited states of Re and Tc complexes
Andrew S Del Negro1, Carl J Seliskar, William R Heineman
1Pacific Northwest National Laboratory, Richland, WA 99352, USA.
Abstract:
Like the Re analogue, the ligand-to-metal charge transfer (LMCT) excited-state of [Tc(dmpe)3]2+ (dmpe is bis-1,2-(dimethylphosphino)ethane) is luminescent in solution at room temperature. Surprisingly, both [M(dmpe)3]2+* species have extremely large excited-state potentials (ESPs) as oxidants-the highest for any simple coordination complex of a transition metal. Furthermore, this potential is available using a photon of visible light (calculated for M = Re(Tc); E1/2* = +2.61(2.52) V versus SCE; lambdamax = 526(585) nm). Using a Rehm-Weller analysis with a series of aromatic hydrocarbons as electron-transfer quenchers, E1/2(Re2+*/Re+) has been determined to be 2.58 V, in good agreement with the calculated value. Both [M(dmpe)3]2+* species are quenched by chloride ion and both can function as excited-state oxidants in water solution.
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