Versatile Pt(II) Pyrazolate Complexes : Emission Tuning via Interplay of Chelate Designs and Stacking Assemblies

Three homoleptic Pt(II) metal complexes [Pt(im^Pz)₂] (1), [Pt(imⁱz)₂] (2), and [Pt(im^Mz)₂] (3) were synthesized from the treatment of Pt(DMSO)₂Cl₂ and functional imidazolyl pyrazole in refluxing tetrahydrofuran (THF). Alternatively, the heteroleptic Pt(II) complexes [Pt(im^Pz)(fppz)] (4), [Pt(imⁱz)(fppz)] (5), and [Pt(im^Mz)(fppz)] (6) were obtained from the treatment of a common intermediate [Pt(fppzH)Cl₂] with a corresponding imidazolyl chelate. Pt(II) complexes 1, 2, and 5 were studied by single-crystal X-ray diffraction to reveal the corresponding packing arrangement in their crystal lattices, among which both homoleptic complexes 1 and 2 formed monomeric species, while heteroleptic 5 aligned as a dimer with a nonbonding Pt···Pt contact of 3.574 Å. Subsequent photophysical examinations showed that the homoleptic 1-3 and heteroleptic 4-6 exhibited the structured sky-blue ππ∗ emission and structureless light-green-emitting metal-metal-to-ligand charge transfer (MMLCT) emission in the solid state, respectively. A shortened Pt···Pt interaction of approximately 0.34-0.35 nm was confirmed in thin films of all heteroleptic Pt(II) complexes 4-6 by grazing-incidence X-ray diffraction (GIXD) analyses. Finally, Pt(II) complex 6 was employed as a dopant in the fabrication of organic light-emitting diode (OLED) devices with varied doping ratios, among which OLEDs with only 1 wt % 6 in the SimCP host exhibited a maximum external quantum efficiency (EQE) of 5.8% and CIE_x,y values of 0.20, 0.31. In contrast, OLEDs using a nondoped architecture (i.e., 100% of 6 in the emitting layer (EML)) achieved a maximum EQE of 26.8%, current efficiency (CE) of 91.7 cd A^-1, and power efficiency (PE) of 80.1 lm·W^-1 and CIE_x,y values of 0.41, 0.55, manifesting their versatility in various degrees of stacking assemblies and hence facile color-tuning capability on OLEDs.