Investigation of the Effect of the Trifluoropropynyl Ligand on Pt(N^C^N)X (X = Cl, C2CF3) Complexes

Abstract

The tuning of the luminescent properties of PtII complexes for possible use in organic light-emitting diodes (OLEDs) and sensing applications is commonly achieved by altering the electronic properties of the ligands. Our group recently demonstrated that the trifluoropropynyl ligand is strongly electron-withdrawing and possibly useful for blueshifting emission. Herein, we report the synthesis of two complexes of this trifluoropropynyl ligand, namely PtLC2CF3 and PtLFC2CF3 (L = 1,3-di(2-pyridyl)benzene; LF = 4,6-difluoro-1,3-di(2-pyridyl)benzene). The PtLC2CF3 complex crystallized in the monoclinic space group P21/n with Z = 4. The PtLFC2CF3 complex crystalized in the triclinic space group P-1 with Z = 2. Changing the tridentate ligand from L to LF resulted in a change in the packing structure, with the latter showing a metallophilic interaction (Pt-Pt distance = 3.3341(3) Å). The solution photophysics of the trifluoropropynyl complexes is compared with that of the corresponding Cl complexes, PtLCl and PtLFCl. Replacement of the chloro ligand with the trifluoropropynyl ligand blueshifted the monomer emission by less than 5 nm but blueshifted the excimer emission peaks by 15–20 nm. The complexes of the trifluoropropynyl ligand also favor the excimer emission more than the complexes of the chloro ligand. The excimer emission is quenched by dissolved oxygen significantly more than the corresponding monomer emission. The excimer emission and monomer emission are well separated, and the ratio of monomer to excimer emission is strongly dependent on oxygen concentration.