The temperature dependence of the emission properties of the compounds [Ru(phen) 2 (3Mptr)] + (1), [Ru(bpy) 2 (bpt)] + (2), [Ru(bpy) 2 (bpzt)] + (3), [{Ru(bpy) 2 } 2 (bpt)] 3 + (4) and [{Ru(bpy) 2 } 2 (bpzt)] 3 + (5) in solution and in tetraethylorthosilicate xerogels is reported. It is shown that the excited state parameters of the compounds are strongly affected by the matrix and are dependent on the initial pH of the gel.