Eilatin Complexes of Ruthenium and Osmium. Synthesis, Electrochemical Behavior, and Near-IR Luminescence
2005-10-31T00:00:00Z (GMT) by
The synthesis and characterization of new Ru(II) and Os(II) complexes of the ligand eilatin (<b>1</b>) are described. The new complexes [Ru(bpy)(eil)<sub>2</sub>]<sup>2+</sup> (<b>2</b>), [Ru(eil)<sub>3</sub>]<sup>2+</sup> (<b>3</b>), and [Os(eil)<sub>3</sub>]<sup>2+</sup> (<b>4</b>) (bpy = 2,2‘-bipyridine; eil = eilatin) were synthesized and characterized by NMR, fast atom bombardment mass spectrometry, and elemental analysis. In the series of complexes [Ru(bpy)<i><sub>x</sub></i>(eil)<i><sub>y</sub></i>]<sup>2+</sup> (<i>x</i> + <i>y</i> = 3), the effect of sequential substitution of eil for bpy on the electrochemical and photophysical properties was examined. The absorption spectra of the complexes exhibit several bpy- and eil-associated π−π* and metal-to-ligand charge-transfer (MLCT) transitions in the visible region (400−600 nm), whose energy and relative intensity depend on the number of ligands bound to the metal center (<i>x</i> and <i>y</i>). On going from [Ru(bpy)<sub>2</sub>(eil)]<sup>2+</sup> (<b>5</b>) to <b>2</b> to <b>3</b>, the d<sub>π</sub>(Ru) → π*(eil) MLCT transition undergoes a red shift from 583 to 591 to 599 nm, respectively. Electrochemical measurements performed in dimethyl sulfoxide reveal several ligand-based reduction processes, where each eil ligand can accept up to two electrons at potentials that are significantly anodically shifted (by ca. 1 V) with respect to the bpy ligands. The complexes exhibit near-IR emission (900−1100 nm) of typical <sup>3</sup>MLCT character, both at room temperature and at 77 K. Along the series <b>5</b>, <b>2</b>, and <b>3</b>, upon substitution of eil for bpy, the emission maxima undergo a blue shift and the quantum yields and lifetimes increase. The radiative and nonradiative processes that contribute to deactivation of the excited level are discussed in detail.