Focused electron beam-induced deposition using the heteroleptic complex (η 3 -C 3 H 5 )Ru(CO) 3 Br as a precursor resulted in deposition of material with Ru content of 23 at. %. Transmission electron microscopy images indicated a nanogranular structure of pure Ru nanocrystals, embedded into a matrix containing carbon, oxygen, and bromine. The deposits were purified by annealing in a reactive 98% N 2 /2% H 2 atmosphere at 300 °C, resulting in a reduction of contaminants and an increase of the Ru content to 83 at. %. Although a significant volume loss of 79% was found, the shrinkage was observed mostly for vertical thickness (around 75%). The lateral dimensions decreased much less significantly (around 9%). Deposition results, in conjunction with previous gasphase and condensed-phase surface studies on the electron-induced reactions of (η 3 -C 3 H 5 )Ru(CO) 3 Br, provide insights into the behavior of allyl, carbonyl, and bromide ligands under identical electron beam irradiation.

Quantum yields for loss of a single CO ligand in alkane solutions were determined for the (η3-allyl)­Ru­(CO)3X complexes, where X = Cl, Br, I. The three complexes had similar quantum yields at λexc = 254 nm, while the quantum yields obtained at 313 nm followed a trend of ΦBr > ΦCl > ΦI. A wavelength dependence of the quantum yields in the order Φ254 < Φ313 < Φ334 was observed for the iodo complex. Very low levels of luminescence were observed for the compounds, demonstrating that radiative decay of the excited states was not competitive with nonradiative processes, including photochemical reactions. Excited states were assigned as MLCT or LF on the basis of solvatochromism and DFT studies.