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

IF 2.4 4区材料科学 Q2 CRYSTALLOGRAPHY Crystals Pub Date : 2024-07-25 DOI:10.3390/cryst14080678

John H. Zimmerman, Benjamin J. Cahill, Wilson M. Thomas, Jackson S. McCarthy, Colin D. McMillen, Paul S. Wagenknecht

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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.

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研究三氟丙炔配体对 Pt(N^C^N)X（X = Cl，C2CF3）配合物的影响

通常是通过改变配体的电子特性来调整 PtII 复合物的发光特性，以用于有机发光二极管（OLED）和传感应用。我们的研究小组最近证明，三氟丙炔配体具有很强的电子吸收性，可能有助于蓝移发射。在此，我们报告了这种三氟丙炔配体的两种配合物的合成，即 PtLC2CF3 和 PtLFC2CF3（L = 1,3-二（2-吡啶基）苯；LF = 4,6-二氟-1,3-二（2-吡啶基）苯）。PtLC2CF3 复合物在 Z = 4 的单斜空间群 P21/n 中结晶。PtLFC2CF3 复合物在三菱空间群 P-1 中结晶，Z = 2。将三叉配体从 L 转变为 LF 会导致堆积结构发生变化，后者显示出亲金属相互作用（铂-铂距离 = 3.3341(3) Å）。三氟丙炔配合物的溶液光物理与相应的 Cl 配合物、PtLCl 和 PtLFCl 的溶液光物理进行了比较。用三氟丙炔配体取代氯配体后，单体发射蓝移不到 5 纳米，但准分子发射峰蓝移了 15-20 纳米。三氟丙炔配体的配合物也比氯配体的配合物更有利于准分子发射。受溶解氧淬灭的准分子发射明显多于相应的单体发射。准分子发射和单体发射分离得很好，单体发射和准分子发射的比例与氧气浓度密切相关。

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来源期刊

Crystals CRYSTALLOGRAPHYMATERIALS SCIENCE, MULTIDIS-MATERIALS SCIENCE, MULTIDISCIPLINARY

CiteScore

4.20

自引率

11.10%

发文量

1527

审稿时长

16.12 days

期刊介绍： Crystals (ISSN 2073-4352) is an open access journal that covers all aspects of crystalline material research. Crystals can act as a reference, and as a publication resource, to the community. It publishes reviews, regular research articles, and short communications. Our aim is to encourage scientists to publish their experimental and theoretical results in as much detail as possible. Therefore, there is no restriction on article length. Full experimental details must be provided to enable the results to be reproduced. Crystals provides a forum for the advancement of our understanding of the nucleation, growth, processing, and characterization of crystalline materials. Their mechanical, chemical, electronic, magnetic, and optical properties, and their diverse applications, are all considered to be of importance.