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Versatile coordinative abilities of perhalophenyl-gold(I) fragments to xantphos: Influence on the emissive properties
Journal of Organometallic Chemistry ( IF 2.3 ) Pub Date : 2020-02-23 , DOI: 10.1016/j.jorganchem.2020.121198
José M. López-de-Luzuriaga , Miguel Monge , M. Elena Olmos , María Rodríguez-Castillo , Inés Soldevilla

Reaction of perhalophenylgold(I) complexes [AuR (tht)] (R = C6Cl2F3, C6Cl5; tht = tetrahydrothiophene) with different number of equivalents of Xantphos (4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene) leads to discrete complexes in which the metal atom displays very different coordination environments. Thus, the ionic complex [Au (Xantphos)2][Au(C6Cl2F3)2] (1) or the neutral [Au(C6Cl5) (Xantphos)] (2) one are obtained when a 1:1 (Au:Xantphos) stoichiometry is used. However, similar compounds [Au2R2 (μ-Xantphos)] (R = C6Cl2F3 (3); C6Cl5 (4)) are synthesized when the amount of gold is increased to a 2:1 ratio. The use of diphosphine Xantphos, which can act as bridging, chelate or even as mono-dentate ligand, together with the use of different perhalophenyl groups bonded to the gold(I) centres, allows the synthesis of cationic tetracoordinate gold(I) fragments (1), mononuclear (2) or dinuclear (34) dicoordinate gold(I) complexes. This structural diversity in the coordination arrangements as well as the different aryl groups present in the molecules directly affect their photophysical properties, giving rise to different luminescent emission energies ranging from 470 to 580 nm and also to a different origin for the electronic transitions related to them such as 3IL (3) to 3MLCT (4) and also a mixture of them 3MLCT/3IL (1 and 2). The experimental photophysical results obtained for these gold(I) complexes were supported by DFT and TD-DFT calculations. On the other hand, the behaviour of these complexes in solution is different, losing their emissive properties for all complexes or displaying the co-existence of different structural arrangements in the case of complexes 1 and 2, as observed through variable-temperature 31P{1H} NMR experiments.



中文翻译:

全卤代苯基金(I)片段对黄药的通用配位能力:对发射性质的影响

全卤苯基金(I)配合物[AuR(tht)](R = C 6 Cl 2 F 3,C 6 Cl 5 ; tht =四氢噻吩)与不同数量当量黄原磷(4,5-双(二苯基膦基)-9)的反应,9-二甲基黄嘌呤)导致金属原子显示出非常不同的配位环境的离散配合物。因此,离子络合物[Au(Xantphos)2 ] [Au(C 6 Cl 2 F 32 ](1)或中性[Au(C 6 Cl 5)(Xantphos)](2)当使用1:1(Au:Xantphos)化学计量比时获得。但是,当金的含量增加到2:1时,会合成类似的化合物[Au 2 R 2(μ-Xantphos)](R = C 6 Cl 2 F 33); C 6 Cl 54))。比。使用二膦黄嘌呤可以起桥连,螯合甚至单齿配体的作用,并结合使用与金(I)中心键合的不同全卤代苯基,可以合成阳离子四配位金(I)片段(1),单核(2)或双核(34)与金(I)配合物相配位。配位结构的这种结构多样性以及分子中存在的不同芳基会直接影响其光物理性质,从而导致产生从470至580 nm范围内的不同发光发射能量,并导致与它们相关的电子跃迁的不同起源例如3 IL(3)至3 MLCT(4)以及它们的混合物3 MLCT / 3 IL(12)。这些金(I)配合物获得的实验光物理结果得到了DFT和TD-DFT计算的支持。另一方面,这些复合物在溶液中的行为是不同的,对于所有复合物,它们的发射特性都丧失了,或者在复合物12的情况下,它们表现出不同结构排列的共存,如通过变温31 P { 1 H NMR实验。

更新日期:2020-02-23
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