Luminescent cuprous complexes are an important class of coordination compounds due to their relative abundance, low cost and ability to display excellent luminescence. The heteroleptic cuprous complex solvate rac‐(acetonitrile‐κN)(3‐aminopyridine‐κN)[2,2′‐bis(diphenylphosphanyl)‐1,1′‐binaphthyl‐κ²P,P′]copper(I) hexafluoridophosphate dichloromethane monosolvate, [Cu(C₅H₆N₂)(C₂H₃N)(C₄₄H₃₂P₂)]PF₆·CH₂Cl₂, conventionally abbreviated as [Cu(3‐PyNH₂)(CH₃CN)(BINAP)]PF₆·CH₂Cl₂, (I), where BINAP and 3‐PyNH₂ represent 2,2′‐bis(diphenylphosphanyl)‐1,1′‐binaphthyl and 3‐aminopyridine, respectively, is described. In this complex solvate, the asymmetric unit consists of a cocrystallized dichloromethane molecule, a hexafluoridophosphate anion and a complete racemic heteroleptic cuprous complex cation in which the cuprous centre, in a tetrahedral CuP₂N₂ coordination, is coordinated by two P atoms from the BINAP ligand, one N atom from the 3‐PyNH₂ ligand and another N atom from a coordinated acetonitrile molecule. The UV–Vis absorption and photoluminescence properties of this heteroleptic cuprous complex have been studied on polycrystalline powder samples, which had been verified by powder X‐ray diffraction before recording the spectra. Time‐dependent density functional theory (TD‐DFT) calculations and a wavefunction analysis reveal that the orange–yellow phosphorescence emission should originate from intra‐ligand (BINAP) charge transfer mixed with a little of the metal‐to‐ligand charge transfer ³(IL+ML)CT excited state.

中文翻译：

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一种由BINAP配体支持的新型杂合磷光亚铜配合物：合成，结构，发光性质和理论分析。

发光的亚铜配合物是一类重要的配位化合物，因为它们相对丰度高，成本低并且具有出色的发光能力。所述杂亚铜络合物溶剂化物外消旋- （乙腈- κ Ñ）（3-氨基吡啶κ Ñ）[2,2'-双（二苯基膦）-1,1'-联萘κ ² P，P ']铜（I）六氟磷酸二氢氯甲烷单溶剂化物，[Cu（C ₅ H ₆ N ₂）（C ₂ H ₃ N）（C ₄₄ H ₃₂ P ₂）] PF ₆ ·CH ₂ Cl ₂，通常缩写为[Cu（3-PyNH ₂）（CH ₃ CN）（BINAP）] PF ₆ ·CH ₂ Cl ₂，（I），其中BINAP和3-PyNH ₂代表2,2'-双（二苯基膦基）分别描述了-1,1'-联萘基和3-氨基吡啶。在这种复杂的溶剂化物中，不对称单元由共结晶的二氯甲烷分子，六氟磷酸根阴离子和完整的外消旋杂配亚铜络合物阳离子组成，其中亚铜中心在四面体CuP ₂ N ₂配位下由来自BINAP的两个P原子配位配体，一个3 PyNH _2中的N原子配体和另一个N原子来自配位乙腈分子。已经在多晶粉末样品上研究了这种杂配亚铜络合物的UV-Vis吸收和光致发光特性，在记录光谱之前已通过粉末X射线衍射对其进行了验证。随时间变化的密度泛函理论（TD-DFT）计算和波函数分析表明，橙黄色磷光发射应源自配体内部（BINAP）电荷转移以及少量金属-配体电荷转移³（ IL + ML）CT激发态。