A spectroelectrochemical sensor consisting of an indium tin oxide (ITO) optically transparent electrode (OTE) coated with a thin film of partially sulfonated polystyrene-blockpoly(ethylene-ran-butylene)-block-polystyrene (SSEBS) was developed for [Tc(dmpe)(3)](+) (dmpe = 1,2-bis(dimethylphosphino)ethane). [Tc(dmpe)(3)](+) was preconcentrated by ion-exchange into the SSEBS film after a 20 min exposure to aqueous [Tc(dmpe)(3)](+) solution, resulting in a 14-fold increase in cathodic peak current compared to a bare OTE. Colorless [Tc(dmpe)(3)](+) was reversibly oxidized to colored [Tc(dmpe)(3)](2+) by cyclic voltammetry. Detection of [Tc(dmpe)(3)](2+) was accomplished through emission spectroscopy by electrochemically oxidizing the complex from nonemissive [Tc(dmpe)(3)](+) to emissive [Tc(dmpe)(3)](2+). The working principle of the sensor consisted of electrochemically cycling between nonemissive [Tc(dmpe)(3)](+) and emissive [Tc(dmpe)(3)](2+) and monitoring the modulated emission (λ(exc) = 532 nm; λ(em) = 660 nm). The sensor gave a linear response over the concentration range of 0.16-340.0 μM of [Tc(dmpe)(3)](2+/+) in aqueous phase with a detection limit of 24 nM.

The luminescence of trans-[TcO2(L)4]+ (L = pyridine (py) or picoline (pic)) and trans-[TcO2(CN)4]3- 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 [TcO2(py)4]BPh4 and [TcO2(pic)4]BPh4 display the characteristic progressions of the symmetric O=Tc=O and Tc-L stretching modes. DFT/TDDFT calculations were performed on the trans-[MO2(L)4]+ (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 mus for the series of Tc complexes are consistent with the Re analogues.

The structures of novel Tc(V) complexes trans-[TcO(2)(py)(4)]Cl·2H(2)O (1a), trans-[TcO(2)(pic)(4)]Cl·2H(2)O (2a), and trans-[TcO(2)(pic)(4)]BPh(4) (2b) were determined by X-ray crystallography, and their spectroscopic characteristics were investigated by emission spectroscopy and atomic scale calculations. The cations adopt a tetragonally distorted octahedral geometry, with a trans orientation of the apical oxo groups. trans-[TcO(2)(pic)(4)]BPh(4) has an inversion center located on technetium; however, for trans-[TcO(2)(py)(4)]Cl·2H(2)O and trans-[TcO(2)(pic)(4)]Cl·2H(2)O, a strong H bond formed by only one of the oxo substituents introduces an asymmetry in the structure, resulting in inequivalent trans Tc-N and Tc═O distances. Upon 415 nm excitation at room temperature, the complexes exhibited broad, structureless luminescences with emission maxima at approximately 710 nm (1a) and 750 nm (2a, 2b). Like the Re(V) analogs, the Tc(V) complexes luminesce from a (3)E(g) excited state. Upon cooling the samples from 278 to 8 K, distinct vibronic features appear in the spectra of the complexes along with increases in emission intensities. The low temperature emission spectra display the characteristic progressions of the symmetric O═Tc═O and the Tc-L stretching modes. Lowest-energy, triplet excited-state distortions calculated using a time-dependent theoretical approach are in good agreement with the experimental spectra. The discovery of luminescence from the trans-dioxotechnetium(V) complexes provides the first opportunity to directly compare fundamental luminescence properties of second- and third-row d(2) metal-oxo congeners.