Linking Re^I and Pt^II Chromophores with Aminopyridines: A Simple Route to Achieve a Complicated Photophysical Behavior

Abstract

The bifunctional aminopyridine ligands H₂ N-(CH₂ )_n -4-C₅ H₄ N (n=0, L1; 1, L2; 2, L3) have been utilized for the preparation of the rhenium complexes [Re(phen)(CO)₃ (L1-L3)]⁺ (1-3; phen=phenanthroline). Complexes 2 and 3 with NH₂ -coordinated L2 and L3, respectively, were coupled with cycloplatinated motifs {Pt(ppy)Cl} and {Pt(dpyb)}⁺ (ppy=2-phenylpyridine, dpyb=dipyridylbenzene) to give the bimetallic species [Re(phen)(CO)₃ (μ-L2/L3)Pt(ppy)Cl]⁺ (4, 6) and [Re(phen)(CO)₃ (μ-L2/L3)Pt(dpyb)]²⁺ (5, 7). In solution, complexes 4 and 6 show ³ MLCT {Re}-based emission at 298 K, which changes to the ³ IL(ppy) state at 77 K. The photophysical properties of compounds 5 and 7 display a pronounced concentration dependence, presumably due to the formation of bimolecular aggregates. Analysis of the spectroscopic data, combined with TD-DFT simulations, suggest that unconventional heteroleptic {Re(phen)}⋅⋅⋅{Pt(dpyb)} π-π stacking operates as the driving force for ground-state association. The latter, together with intra- and intermolecular energy-transfer processes, determines the appearance of multiple emission bands and results in nonlinear relaxation kinetics of the excited states.