Enhanced blue phosphorescence in platinum acetylide complexes <i>via</i> a secondary heavy metal and anion-controlled aggregation

Organoplatinum compounds represent a promising class of blue-phosphorescent molecules for electroluminescent color displays. Much recent work has focused on decreasing the nonradiative rate constant (<i>k</i> _nr) to improve the photoluminescence quantum yield (<i>Φ</i> _PL) of these compounds, but in most cases small radiative rate constants (<i>k</i> _r) lead to long excited-state lifetimes (<i>τ</i>) poorly suited for electroluminescence applications. In this work, we present an approach to increase <i>k</i> _r and <i>Φ</i> _PL in blue-phosphorescent platinum acetylide complexes with the general formula <i>cis</i>-[Pt(CN-R)₂(C[triple bond, length as m-dash]C-2-py)₂] (CN-R is an alkyl isocyanide and C[triple bond, length as m-dash]C-2-py is 2-pyridylacetylide). This method incorporates secondary heavy metals, Cu(i) or Ag(i), bound by the pyridyl moieties. We observe the formation of dimer complexes in the solid state due to noncovalent interactions between the secondary metal and the acetylide ligands, especially strong in the case of Cu(i). Incorporation of Cu(i) also erodes the desired blue-phosphorescence by introducing a low-lying metal-to-ligand charge transfer (³MLCT) state that dominates the observed phosphorescence. In the complexes bound to Ag(i), we find that phosphorescence profile is strongly dependent on the counteranion, which we propose is caused by different degrees of aggregation. With this insight, we show that coordination of AgBAr^F ₄ (BAr^F ₄ ^- = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate), with a large noncoordinating counteranion, inhibits aggregation and results in a 4-8× increase in <i>k</i> _r and a 5-10× increase in <i>Φ</i> _PL while preserving a pure blue phosphorescence profile.