Clean singlet oxygen production by a Re

Abstract

© 2015 American Chemical Society.Rhenium complexes are versatile molecular building blocks whose tunable photophysical properties are useful in diverse opto-related applications. Herein we report the synthesis and characterization of a novel Re<sup>I</sup> tricarbonyldiimine complex, [(phen)Re(CO)<inf>3</inf>Br] (phen: 1,10-phenanthroline), which was found to be an efficient singlet oxygen [O<inf>2</inf>(<sup>1</sup>Î"<inf>g</inf>)] photosensitizer in homogeneous solution [Φ<inf>O</inf><inf>2</inf>(<sup>1</sup>Î"g) = 0.55 (dichloromethane) and 0.16 (dimethylformamide)]. The photophysical properties of [(phen)Re(CO)<inf>3</inf>Br] were thoroughly characterized in solution and modeled by means of density functional theory (DFT) and time-dependent (TD)-DFT quantum mechanical calculations. The Re complex was incorporated into a flexible polymeric silsesquioxane (SSO) film, which has excellent dopant compatibility, chemical resistance, and mechanical properties. When [(phen)Re(CO)<inf>3</in