RESONANT LUMINESCENCE LINE NARROWING OF THE R-LINES IN [RH(BPY)3](PF6)3-CR(III)

A rigorous study of the R line luminescence of the title compound is presented. From site-selective spectroscopy. the temperature dependence of the luminescence, and the homogeneous line width of the R2 line, a 18.5 cm-1 2E splitting for the majority sites of the title compound is confirmed. About 20% of the Cr(bpy)3(3+) chromophores are in slightly different sites leading to a variation of the 2E splitting of about 10%. From resonant FLN experiments in external magnetic fields up to 3 T a g(parallel-to) = - 1.76 +/- 0.01 value of the lowest-excited state, 2E(EBAR), is deduced. Relatively large homogeneous line widths of 0.01 and 1.8 cm-1 are found for the R1 and R2 lines at 1.5 K, respectively. The direct relaxation process between the split 2E components is the main contribution to the widths of the R lines between 10 and 100 K.