Solvent-Free Thermal Synthesis of Luminescent Dinuclear Cu(I) Complexes with Triarylphosphines
Solvent-Free Thermal Synthesis of Luminescent Dinuclear Cu(I) Complexes with Triarylphosphines
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DOI：
10.1021/acs.inorgchem.8b00439
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发表时间：
2018-05-21
影响因子：
4.6
通讯作者：
Kato, Masako
中科院分区：
文献类型：
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作者：
Liang, Panyi;Kobayashi, Atsushi;Kato, Masako
通过溶液反应和罕见报道的无溶剂热法制备了发光 [Cu2I2(pyrpy)(2)(PR3)(2)] 配合物（pyrpy = 4-吡咯烷吡啶；PR3 = 三苯基膦 (1)、三间甲苯基膦 (2)、三对甲苯基膦 (3)）。 X射线结构分析表明，形成了由两个PR3和两个pypy配体包围的双核{Cu2I2}核心组成的配合物。虽然吡啶的熔点是本研究中使用的有机单元中最低的，但通过热合成方法制备的发光双核络合物所需的温度很大程度上取决于 PR3 部分。通过无溶剂热法成功制备了三种配合物中的两种（1和3）。配合物 1-3 在 450 nm 附近表现出蓝色发射，量子产率 (Phi) 分别为 0.24、0.31 和 0.51。发射寿命测量和时间相关密度泛函理论 (TD-DFT) 计算表明每个复合物中存在热激活延迟荧光 (TADF)。这种 TADF 材料的无溶剂热合成代表了一种直接在薄层电子器件（例如有机发光二极管）的基板上制备发光层的有前途的方法。
Luminescent [Cu2I2(pyrpy)(2)(PR3)(2)] complexes (pyrpy = 4-pyrrolidinopyridine; PR3 = triphenylphosphine (1), tri-m-tolylphosphine (2), tri-p-tolylphosphine (3)) were prepared by solution reactions and a rarely reported solvent-free thermal method. X-ray structure analyses reveal that complexes composed of dinuclear {Cu2I2} cores surrounded by two PR3 and two pyrpy ligands were formed. Although the melting point of pyrpy is the lowest among the organic units used in this study, the temperature required to form the luminescent dinuclear complex, prepared by the thermal synthesis method, depended strongly on the PR3 moiety. Two of the three complexes (1 and 3) were successfully prepared by the solvent free thermal method. Complexes 1-3 exhibited blue emissions at around 450 nm with moderately high quantum yields (Phi) of 0.24, 0.31, and 0.51, respectively. Emission-lifetime measurements and time-dependent density functional theory (TD-DFT) calculations suggest thermally activated delayed fluorescence (TADF) in each complex. This solvent-free thermal synthesis of TADF materials represents a promising method for the preparation of luminescent layers directly onto substrates of thin-layer electronic devices, such as organic light-emitting diodes.