Tuesday, 27 June 2006
Ponderosa (poster/exhibit) (John Ascuaga’s Nugget Casino Resort)
159

Characterization of trans-dioxotechnetium(V) and technetium(II)phosphine excited states and spectroelectrochemical detection of pertechnetate

Samuel Bryan1, Andrew S. Del Negro1, Zheming Wang1, Timothy L. Hubler1, William R. Heineman2, Carl J. Seliskar3, and B. Patrick Sullivan4. (1) Pacific National Laboratories, Richland, WA, (2) University of Cincinnati, OH, Cincinnati, OH, (3) University of Cincinnati, Cincinnati, OH, (4) University of Wyoming, Laramie, WY

We report the first examples of excited-state luminescence from technetium complexes. We have examined a series of trans-dioxo complexes of Tc(V) and a Tc(I/II) phosphine complex and compare their respective photophysical properties with the corresponding rhenium analogues.

When excited with a 415 nm laser, the Tc(V) complexes luminesce in the 700-800 nm range and have excited state lifetimes in the range of several microseconds at room temperature. The low-temperature luminescence spectra of the technetium complexes have also been investigated. Distinct vibrational band progressions are resolved in the low-temperature luminescence spectra. Excited state lifetimes at 5 K vary between tens of microseconds to several milliseconds for the dioxo-technetium complexes.

In addition, a previously known Tc(I) complex, [Tc(DMPE) 3]+ which has been used as a radiography imaging agent has been demonstrated in our labs to fluoresce in the visible wavelength region upon a one-electron reversible oxidation to form the Tc(II), [Tc(DMPE)3]2+ complex in aqueous solution. The luminescence of [Tc(DMPE)3]2+ was observed by illuminating the solution complex with a 404 nm excitation while performing the reversible electrochemical experiment. In a recent application, we have focused on making thin chemically-selective films for sensing radioactive technetium compounds and in this effort have developed a fluorescence-based spectroelectrochemical sensor.

Characterization of the new dioxo-technetium(V) and technetium(II)phosphine excited states as well as application of the respective chromophores for use in a spectroelectrochemical sensor for pertechnetate will be discussed.


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