Study of cycloplatinated complexes with isocyanide ligands: isomerism, optical properties and mechanochromism

Resumen

Platinum(II) cyclometalated derivatives have attracted a great interest dueto their rich photophysical properties, with interesting applications aschemical sensors, photocatalysts or in light emitting diodes (OLEDs). Thepresence of planar ligands in these complexes improves the luminescenceand the ability to form aggregates through the formation of Pt···Pt and/orπ···π interactions. In this context, there are very scarce examples ofheteroleptic complexes with isocyanide and alkynyl ligands.In this work, we present the synthesis and characterization of a group ofPt(II) compounds featuring 2-phenylpyridine and 2-phenylquinoline ascyclometalated ligands and 2,6-dimethylphenyl isocyanide as auxiliaryligand. The p-tolylacetylide complexes [Pt(C^N)(C≡CTol)(C≡NXyl)] (C^N =ppy 3, pq 4) have been obtained from the chloride derivatives[Pt(C^N)Cl(C≡NXyl)] (C^N = ppy 1, pq 2). The isomerism of thesecompounds in which the isocyanide ligand can be trans to the nitrogen or tothe carbon of the cyclometalated ligand has been determined by differenttechniques, as NMR and X-ray diffraction.The photophysical properties (absorption and emission) of all complexeshave been studied with the aid of theoretical calculations. Interestingly, thephenylpyridine derivatives exhibit mechanical stimuli responsive colour andluminescence changes correlated with the formation of different aggregateswith π···π and/or Pt···Pt interactions.