Abstract

In our attempts to identify new species in the preparation of copper(I)-Dppm (Dppm = bis(diphenylphosphino)methane) complexes under the condition of excess Dppm, we isolated and analyzed a new binuclear copper(I)-Dppm complex, namely, [(μ₂-η¹,η¹-Dppm)₂Cu₂(η¹-Dppm)₂(μ₂-Cl)](BF₄) (I). We report here the synthesis, crystal structure (CIF file CCDC no. 1912269), characterizations by various spectroscopic (IR, ¹HNMR, UV−Vis, powder XRD) techniques and the thermal and luminescent properties of this complex. Its X-ray crystal structure reveals a discrete cationic binuclear copper(I)-Dppm (1 : 2) species for the first time. The binuclear copper centres are bridged by a pair of cis-Dppm molecules and one chloride ion, and further consolidated by two trans-Dppm molecules in mono-dentate fashion. It exhibits cyan photoluminescence in the solid state at room temperature. This work not only addresses the concern of structural information of binuclear copper(I)-Dppm (1 : 2) complex, but also provides a new way to incorporate sterically hindered ligands into the {Cu(μ₂-η¹,η¹-trans-Dppm)₂Cu} scaffold for novel luminous properties.

中文翻译：

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新型双核铜（I）双（二苯基膦基）甲烷（1：2）配合物的配位和光化学

摘要

在尝试在过量Dppm的条件下识别制备铜（I）-Dppm（Dppm =双（二苯基膦基）甲烷）配合物的新物种时，我们分离并分析了一种新的双核铜（I）-Dppm配合物，即，[（μ ₂ -η ¹，η ¹ -Dppm）₂的Cu ₂（η ¹ -Dppm）₂（μ ₂ -Cl）]（BF ₄）（我）。我们在这里报告了合成，晶体结构（CIF文件CCDC 1912269），各种光谱学的表征（IR，¹HNMR，UV-Vis，粉末XRD）技术以及该配合物的热和发光性质。它的X射线晶体结构首次显示出离散的阳离子双核铜（I）-Dppm（1：2）物种。双核铜中心被一对顺式-Dppm分子和一个氯离子桥接，并被两个反式-Dppm分子以单齿方式进一步固结。它在室温下呈固态呈现青色光致发光。这项工作不仅解决了双核铜的结构信息的关注（I）-Dppm（1:2）复合物，但也提供并入空间位阻的配体到{铜（μ的新方式₂ -η ¹，η ¹ -反-Dppm）₂ Cu}支架具有新颖的发光特性。