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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >The influence of thiolate ligands on the luminescence properties of cycloplatinated(II) complexes
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The influence of thiolate ligands on the luminescence properties of cycloplatinated(II) complexes

机译：硫醇酸酯配体对依挥（II）复合物发光性质的影响

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摘要

Complexes [Pt(C<^>N)(PPh3)Cl] (C<^>N = bzq (7,8-benzoquinolinyl, A) and ppy (2-phenylpyridinyl, B)) were reacted with various thiolate ligands to afford complexes [Pt(C<^>N)(PPh3)(kappa(1)-S-SR)], C<^>N = bzq, R = SPh (thiophenolate, 1a); C<^>N = ppy, R = SPh (1b); C<^>N = bzq, R = Spy (pyridine-2-thiolate, 2a); C<^>N = ppy, R = Spy (2b); C<^>N = bzq, R = SpyN (pyrimidine-2-thiolate, 3a); C<^>N = ppy, R = SpyN (3b). Complexes 1-3 were characterized by NMR spectroscopy, and the solid-state structures of 1a and 2a were determined by X-ray diffraction methods. Replacing a chloride ligand with electron-rich thiolates changes the lowest energy singlet and triplet excited states to the ones that feature charge transfer from the thiolate (mixed with some metal character) to the C<^>N ligand, which was supported by TD-DFT calculations. All complexes are emissive at 298 K in the solid state except 2b and 3b, which are emissive only at 77 K having a less rigid structure compared to others. The emission of 1a and 1b originates from a low-energy excited state of d(Pt)/pi(SR) -> pi* C<^>N while 3a exhibits a (LC)-L-3/(MLCT)-M-3 transition. For 1a and 1b, the radiative rate and the quantum efficiency are higher in a rigid environment such as a solid compared to a polymer and solution. Decreasing the rigidity of the environment leads to a flexibility of rotation of the -SR around the axis of the Pt-S bond. So the geometry can be easily changed after radiation and the lowest lying triplet excited state would have the effective contribution of the dd* transition, which opens a nonradiative pathway at room temperature.
机译：复合物[Pt（C <^> n）（PPH3）Cl]（C = N = BZQ（7,8-苯并喹啉基，A）和PPY（2-苯基吡啶基，B））与各种硫醇酸盐配体反应复合物[Pt（c <^> n）（pph3）（κ（1）-s-sr）]，c <^> n = bzq，r = spH（噻吩酚，1a）; c <^> n = ppy，r = sph（1b）; C <^> n = BZQ，R = SPY（吡啶-2-硫醇，2a）; c <^> n = ppy，r = spy（2b）; C n = ppy，r = spyn（3b）。通过NMR光谱表征复合物1-3，并且通过X射线衍射方法测定1A和2A的固态结构。用富含电子硫醇酸盐替换氯化物配体将最低能量单态和三重态激发状态改变为从硫醇（与一些金属特征混合）到C + N配体的电荷转移的那些，该液体均为TD-的C <^> N配体DFT计算。除了2B和3B之外，所有复合物在298 k下发射，除了2B和3B，仅以77 k为77 k，与他人相比具有较小的结构。 1a和1b的发射来自D（pt）/ pi（sr） - > pi * c <^> n的低能量激发状态，而3a呈现a（lc）-1-3 /（mlct）-m -3过渡。对于图1A和1B，与聚合物和溶液相比，诸如固体的刚性环境中，辐射速率和量子效率较高。降低环境的刚度导致-SR围绕PT-S键的轴线旋转的柔韧性。因此，在辐射之后可以容易地改变几何形状，并且最低的平三态激发状态将具有DD *过渡的有效贡献，其在室温下打开非散路通路。

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