一种 C^N 环铂(II)氟化物配合物：光物理研究和 C-F 键形成。
A C^N Cycloplatinated(II) Fluoride Complex: Photophysical Studies and C-F Bond Formation.
机构信息
Department of Chemistry and Biochemistry, University of Arkansas, Fayetteville, Arkansas 72701, United States.
Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan 45137-66731, Iran.
出版信息
Inorg Chem. 2020 Nov 16;59(22):16319-16327. doi: 10.1021/acs.inorgchem.0c02115. Epub 2020 Nov 2.
Abstract
This work reports the synthesis and characterization of a new C^N-based cycloplatinated(II) fluoride complex, [Pt(ppy)(PPh)F] (; ppy = 2-phenylpyridinate), involving a Pt-F bond. The new complex is highly luminescent in the green area with a high quantum yield of 94.6% at 77 K. A comparison study of the heavier halogen derivatives reveals a descending emission quantum yield order of F > Cl > Br > I. Time-dependent density functional theory calculations ascribe the decreased emission efficiency to the decreasing trend of an intraligand (IL) transition from F to I, which accounts for the major radiative pathway. In addition, is capable of the fluorinating alkyl halides, leading to C-F bond formation at room temperature.
摘要
本工作报道了一种新型的基于 C^N 的环铂(II)氟化物配合物[Pt(ppy)(PPh)F]（;ppy=2-苯基吡啶酸盐）的合成与表征，其中涉及 Pt-F 键。该新型配合物在绿光区域具有很高的荧光，在 77 K 时量子产率高达 94.6%。较重卤素衍生物的比较研究表明，发射量子产率的顺序为 F > Cl > Br > I。含时密度泛函理论计算将发射效率的降低归因于从 F 到 I 的配体内（IL）跃迁的降低趋势，这是主要的辐射途径。此外，[Pt(ppy)(PPh)F]还能够氟化烷基卤化物，在室温下形成 C-F 键。
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