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Unexpected formation of a fused double cycle trinuclear gold(i) complex supported by ortho-phenyl metallated aryl-diphosphine ligands and strong aurophilic interactions

机译:意外形成的稠合双环三核金(i)配合物由邻苯基金属化的芳基-二膦配体和强亲金相互作用支撑

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摘要

The first homoleptic trinuclear arylgold(i) complex, [Au3(L')2](NO3) (3), based on an ortho-phenyl metallated aryl-diphosphine ligand (L' = o-C6H4PPh(C15H10O)PPh2), has been obtained through a new thermolytic reaction of the corresponding diauracycle, [Au2(L)2](NO3)2 (L = xantphos). The formation of 3 involves activation of the ortho-phenyl C-H bond of the xantphos ligands. The presence of Au-C bonds in this new gold-diphosphine cluster is not its only remarkable feature, since it also displays two 12-membered rings fused together and a linear {Au3} chain with aurophilic interactions. Complex 3 exhibits strong sky-blue luminescence that can be assigned to a triplet metal-metal (3MM) transition partially mixed with a ligand-to-metal-metal charge transfer (3LMMCT) transition related to the aurophilic bonding. This [Au3(L')2]+ triauracycle also shows AIEE-activity, and is a selective luminescent chemosensor for metal ions.
机译:基于邻苯基金属化的芳基-二膦配体(L'= o-C6H4PPh(C15H10O)PPh2)的第一个均质三核芳基金(i)络合物[Au3(L')2](NO3)(3)具有通过相应的二氮杂环[Au2(L)2](NO3)2(L = xantphos)的新热解反应获得了苯二酚。 3的形成涉及黄磷配体的邻苯基C-H键的激活。在这个新的金-二膦簇中,Au-C键的存在不是其唯一的显着特征,因为它还显示出两个稠合在一起的12元环和具有亲金相互作用的线性{Au3}链。配合物3表现出很强的天蓝色发光,可将其分配给三重态金属-金属(3MM)过渡部分与与亲金键合相关的配体-金属-金属电荷转移(3LMMCT)过渡部分混合。该[Au3(L')2] +三氟环也显示出AIEE活性,是金属离子的选择性发光化学传感器。

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