Tuning the Excimer Emission of Amphiphilic Platinum(II) Complexes Mediated by Phospholipid Vesicles

Two new amphiphilic platinum­(II) complexes, [Pt­(2-(4-fluorophenyl)-5-(4-dodecyloxyphenyl)­pyridine) (acac)] (Pt-1) and [Pt­(2-(4-dodecyloxyphenyl)-5-(thien-2-yl)-c-cyclopentenepyridine) (acac)] (Pt-2), where acac is acetylacetonate, were synthesized and characterized. Apart from conventional phosphorescence of single molecules (MEmonomer emission), complexes Pt-1 and Pt-2 also exhibit excimer emission (EE) when embedded into phospholipid vesicles, that is assigned to emissive Pt–Pt excimers. The EE intensity in vesicular media appeared to depend on the viscosity of the vesicles and the concentration of the embedded complex. Differences in the EE properties of complexes Pt-1 and Pt-2 are correlated with the energies of the π-character frontier orbitals defined by the design of the cyclometalating phenylpyridine ligand. Higher energies of the frontier π-orbitals (HOMO and LUMO) naturally promote stronger π–π interactions, thus obstructing the PtII–PtII interaction.