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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Dual ligand-based fluorescence and phosphorescence emission at room temperature from platinum thioxanthonyl complexes
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Dual ligand-based fluorescence and phosphorescence emission at room temperature from platinum thioxanthonyl complexes

机译：铂硫氧杂蒽醌配合物在室温下基于双配体的荧光和磷光发射

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摘要

New square-planar platinum(II) complexes of the type trans-[Pt(PEt3)(2)(Tx)(X)] (X = Br, Cl, I or CN) bearing a sigma-bonded thioxanthon-2-yl (Tx) ligand have been prepared and characterised by X-ray crystallography, cyclic voltammetry, and by NMR and electronic absorption and luminescence spectroscopy. The ligand X hardly influences the electronic transitions, which indicates that the relevant molecular orbitals are largely confined to the Pt-Tx chromophore. In agreement with TD-DFT calculations the energetically lowest electronic transition is assigned as the Tx-centred pi-pi* HOMO --> LUMO excitation. All four complexes display dual emission from the sigma-bonded Tx ligand at ca. 450 nm and at ca. 510 nm, which are assigned as fluorescence originating from the (1)pi(star)-state and as phosphorescence originating from the (3)pi(star)-state, respectively. The phosphorescence quantum yield increases with increasing sigma-donor strength of the ligand X and reaches a uniquely high value of 18.8% for the chlorido complex Pt-Cl. Switching-on of Tx phosphorescence emission by the Pt(PEt3)(2)(X) fragment goes along with a reduction of the lifetime of the Tx triplet state from several ms in purely organic derivatives to ca. 2 mu s in the complexes.
机译：新型反式[Pt（PEt3）（2）（Tx）（X）]（X = Br，Cl，I或CN）的正方形平面铂（II）配合物，其结合有σ-键合的硫氧杂蒽-2-基（Tx）配体已通过X射线晶体学，循环伏安法，NMR，电子吸收和发光光谱法进行了制备和表征。配体X几乎不影响电子跃迁，这表明相关的分子轨道在很大程度上限于Pt-Tx发色团。与TD-DFT计算一致，能量最低的电子跃迁被指定为以Tx为中心的pi-pi * HOMO-> LUMO激发。所有这四个复合物在σ处都显示出与sigma键合的Tx配体的双重发射。 450 nm左右510 nm，分别被指定为源自（1）pi（star）态的荧光和源自（3）pi（star）态的磷光。磷光量子产率随配体X的sigma-donor强度的增加而增加，并且对于氯配合物Pt-Cl达到18.8％的独特高值。 Pt（PEt3）（2）（X）片段打开Tx磷光发射的同时，Tx三重态的寿命也从纯有机衍生物中的几ms缩短到了大约1 ms。在复杂的2亩。

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