10.1021/ja054906m.s001
Andrew S. Del Negro
Andrew
S. Del Negro
Zheming Wang
Zheming
Wang
Carl J. Seliskar
Carl J.
Seliskar
William R. Heineman
William R.
Heineman
B. Patrick Sullivan
B. Patrick
Sullivan
Sean E. Hightower
Sean E.
Hightower
Timothy L. Hubler
Timothy L.
Hubler
Samuel A. Bryan
Samuel A.
Bryan
Luminescence from the <i>trans</i>-Dioxotechnetium(V) Chromophore
American Chemical Society
2005
Re
analogue
tran
BPh 4 display
Tc complexes
MO
py
TcO 2
CN
DFT
pic
nm
emission
luminescence
2005-11-02 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Luminescence_from_the_i_trans_i_Dioxotechnetium_V_Chromophore/3259561
The luminescence of <i>trans</i>-[TcO<sub>2</sub>(L)<sub>4</sub>]<sup>+</sup> (L = pyridine (py) or picoline (pic)) and <i>trans</i>-[TcO<sub>2</sub>(CN)<sub>4</sub>]<sup>3-</sup> at room and low temperature is described and represents the first example of room temperature excited-state luminescence observed for Tc complexes. At room temperature, the complexes exhibited broad luminescence with emission maxima ranging from 745 to 780 nm. Analogous to the Re complexes (emission at 635−655 nm), the low-temperature emission spectra of microcrystalline samples of [TcO<sub>2</sub>(py)<sub>4</sub>]BPh<sub>4</sub> and [TcO<sub>2</sub>(pic)<sub>4</sub>]BPh<sub>4</sub> display the characteristic progressions of the symmetric OTcO and Tc−L stretching modes. DFT/TDDFT calculations were performed on the <i>trans</i>-[MO<sub>2</sub>(L)<sub>4</sub>]<sup>+</sup> (M = Re, Tc) congeners and predicted the dioxotechnetium emission to be 0.41 eV lower in energy than its Re analogue. Low-temperature lifetimes (8 K) ranging from 15 to 1926 μs for the series of Tc complexes are consistent with the Re analogues.