氟化β-二酮配体的单金属和双金属铂配合物,Inorganic Chemistry

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氟化β-二酮配体的单金属和双金属铂配合物
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2017-11-07 00:00:00 , DOI: 10.1021/acs.inorgchem.7b02438
Ku Sun Choung ₁ , Mohammad Din Islam ₁ , Richard W. Guo ₁ , Thomas S. Teets ₁

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本文介绍了两种不同的氟化β-二酮（NacNac）配体与环金属化铂的配合物。环金属化铂二聚体[Pt（C ^ N）（μ-X）] _2的反应[C ^ N = 2-苯基吡啶（ppy），2-（2,4-二氟苯基）吡啶（F ₂ppy）; X = Cl，Br]与骨架氟化的β-二酮基配体的锂盐一起生成两种结构类型，具体取决于反应温度。在较温和的温度（<80°C）下，主要产物是不同寻常的卤化物桥联的二铂配合物，证明了桥接两个铂中心的独特的NacNac结合方式。在更高的温度（> 100°C）下，主要物质是Pt（C ^ N）（NacNac）型的单铂配合物。配合物在其循环伏安图中显示的还原波处于适度的电势，以及强烈的可见吸收带（λ> 500 nm），其最小程度地取决于C ^ N配体的身份，或者对于双金属配合物而言，桥接卤化物的身份。此外，单铂配合物在红色和近红外区域显示出结构化的发光，从而形成以NacNac为中心的三重态。所有这些观察结果表明，在具有理想的基于配体的氧化还原和光学性质的配合物的设计中，NacNacπ系统对边界轨道作出了重大贡献，并激发了对氟化β-二酮代配体的持续探索。

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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.

更新日期：2017-11-07

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