Monometallic and Bimetallic Platinum Complexes with Fluorinated β-Diketiminate Ligands

Presented here are complexes of two different fluorinated β-diketiminate (NacNac) ligands with cyclometalated platinum. Reaction of the cyclometalated platinum dimers [Pt(C^N)(μ-X)]₂ [C^N = 2-phenylpyridine (ppy), 2-(2,4-difluorophenyl)pyridine (F₂ppy); X = Cl, Br] with lithium salts of backbone-fluorinated β-diketiminate ligands produces two structure types, depending on the temperature of the reaction. At milder temperatures (<80 °C), the major product is an unusual halide-bridged diplatinum complex, demonstrating a unique NacNac binding mode bridging the two platinum centers. At higher temperatures (>100 °C), the major species is a monoplatinum complex of the type Pt(C^N)(NacNac). The complexes display reduction waves in their cyclic voltammograms at mild potentials, as well as intense visible absorption bands (λ > 500 nm), that depend minimally on the identity of the C^N ligand or, in the case of the bimetallic complexes, the identity of the bridging halide. In addition, the monoplatinum complexes exhibit structured luminescence in the red and near-infrared regions deriving a NacNac-centered triplet state. All of these observations suggest that the NacNac π system contributes substantially to the frontier orbitals and motivates continued exploration of fluorinated β-diketiminate ligands in the design of complexes with desirable ligand-based redox and optical properties.