MARY spectroscopy is finding increasing use in the studies of transient organic radical ions and their reactions. Extending this technique to organometallic species will broaden the class of potential target compounds and can help answer important mechanistic questions in organometallic and spin chemistry. We probed this approach using a tailored Zn(hfac)(2)(PPO)(2) complex. The synthesized complex has quantum yield and fluorescence lifetime (n-decane solution) phi similar to 0.8 and tau similar to 1.3 ns, respectively. For this type of complex it is the first observation of MARY spectra different from those of free ligand, thus implying participation of the complex in the development of the observed signal. (C) 2011 Elsevier B. V. All rights reserved.