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首页> 外文期刊>Chemistry: A European journal >Solid-State luminescence of Au-Cu-Alkynyl complexes induced by metallophilicity-driven aggregation
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Solid-State luminescence of Au-Cu-Alkynyl complexes induced by metallophilicity-driven aggregation

机译：嗜金属性聚集诱导的Au-Cu-炔基配合物的固态发光

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摘要

A new series of homoleptic alkynyl complexes, [{Au_2Cu _2(C_2R)4}n] (R=C_3H_7O (1), C _6H_(11)O (2), C9H19O (3), C_(13)H_(11)O (4)), were obtained from Au(SC_4H_8)Cl, Cu(NCMe)4PF6, and the corresponding alkyne in the presence of a base (NEt3). Complexes 1-4 aggregate upon crystallization into polymeric chains through extensive metallophilic interactions. The cluster that contains fluorenolyl functionalities, C _(13_H_9O (5), crystallizes in its molecular form as a disolvate, [Au_2Cu_2(C_2C_(13)H _9O)_4].2THF. The substitution of weakly bound THF molecules with pyridine molecules leads to the complex [Au2Cu2- (C_2C _(13)H_9O)_4].2py (6), thus giving two polymorphs in the solid state. Such structural diversity is established through metal-chain and hydrogenbond formation, which depends on the stereochemical characteristics of the organic ligands. More interestingly, this solid-state structural arrangement affords good emission properties, such as intensity and spectroscopic profile, which are otherwise very weakly emissive in solution. Metallophilic aggregation of the {Au_2Cu_2} cluster units, as observed in the crystals, results in dramatic enhancement of the room-temperature phosphorescence, thereby reaching a maximum quantum efficiency of 95% (4). A theoretical approach further indicates a synergistic effect of the array of the metal chain upon aggregation, which greatly enhances the spin-orbit coupling and, hence, the phosphorescence, thereby opening up a new direction in the field of aggregateenhanced emission.
机译：一系列新的纯合炔基络合物[{Au_2Cu _2（C_2R）4} n]（R = C_3H_7O（1），C _6H_（11）O（2），C9H19O（3），C_（13）H_（11） O（4））是在碱（NEt3）存在下从Au（SC_4H_8）Cl，Cu（NCMe）4PF6和相应的炔烃获得的。配合物1-4通过广泛的亲金属相互作用结晶成聚合物链后聚集。包含氟烯丙基官能团C _（13_H_9O（5））的分子簇以二溶剂化物[Au_2Cu_2（C_2C_（13）H _9O）_4] .2THF的分子形式结晶。弱结合的THF分子被吡啶分子取代导致形成复合物[Au2Cu2-（C_2C _（13）H_9O）_4] .py（6），从而得到两个固态的多晶型物，这种结构多样性是通过金属链和氢键形成而建立的，这取决于立体化学特征更有趣的是，这种固态结构排列提供了良好的发射特性，例如强度和光谱分布，否则它们在溶液中的发射非常微弱。 ，导致室温磷光显着增强，从而达到最大量子效率95％（4）。一种理论方法进一步表明了金属阵列的协同效应聚集时，它极大地增强了自旋轨道耦合，从而增强了磷光，从而为聚集增强发射领域开辟了新的方向。

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