古巴烷二聚：Cu4 与 Cu8 碘化铜簇,Inorganic Chemistry

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古巴烷二聚：Cu4 与 Cu8 碘化铜簇
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2023-10-23 , DOI: 10.1021/acs.inorgchem.3c02634
Raquel Utrera-Melero ₁ , Marie Cordier ₂ , Florian Massuyeau ₁ , Jean-Yves Mevellec ₁ , Aydar Rakhmatullin ₃ , Charlotte Martineau-Corcos _{3,

4} , Camille Latouche ₁ , Sandrine Perruchas ₁

Affiliation

卤化铜以其结构多样性和丰富的光致发光特性而闻名，在固态照明技术的发展方面显示出巨大的潜力。报道了一系列基于[Cu ₄ I _{4 ]立方烷几何结构的四分子碘化铜簇。}其中，还合成了由四核对应物二聚化产生的罕见几何形状的[Cu ₈ I _{8 ]八核簇。}研究了两种不同的膦配体，它们带有苯乙烯或乙基。因此，研究了二聚化和配体性质对所得簇的光物理性质的影响。通过单晶 X 射线衍射 (SCXRD)、固态核磁共振 (NMR)、红外和拉曼分析来分析结构差异。与乙基相比，苯乙烯官能团似乎极大地影响了团簇的光物理性质。通过密度泛函理论（DFT）计算合理化了乙基衍生物的发光热致变色性质和具有苯乙烯官能团的团簇的有趣的光物理性质。因此，苯乙烯基团显着降低了空轨道的能量，从而影响了团簇的整体能量布局。这项研究发现，碘化铜簇的核性最终对光物理性质的影响小于配体性质的影响。因此，在开发用于特定照明应用的材料时，应考虑适当配体的设计。

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Cubane Dimerization: Cu4 vs Cu8 Copper Iodide Clusters

Copper(I) halides are well-known for their structural diversity and rich photoluminescence properties, showing great potential for the development of solid-state lighting technology. A series of four molecular copper iodide clusters based on the [Cu₄I₄] cubane geometry is reported. Among them, [Cu₈I₈] octanuclear clusters of rare geometry resulting from dimerization of the tetranuclear counterparts were also synthesized. Two different phosphine ligands were studied, bearing either a styrene or an ethyl group. Therefore, the effect of the dimerization and of the ligand nature on the photophysical properties of the resulting clusters is investigated. The structural differences were analyzed by single-crystal X-ray diffraction (SCXRD), solid-state nuclear magnetic resonance (NMR), infrared, and Raman analyses. Compared to the ethyl group, the styrene function appears to greatly impact the photophysical properties of the clusters. The luminescence thermochromic properties of the ethyl derivatives and the intriguing photophysical properties of the clusters with styrene function were rationalized by density functional theory (DFT) calculations. Thus, the styrene group significantly lowers in energy the vacant orbitals and consequently affects the global energetic layout of the clusters. From this study, it was found that the nuclearity of copper iodide clusters eventually has less influence on the photophysical properties than the nature of the ligand. The design of proper ligands should therefore be considered when developing materials for specific lighting applications.

更新日期：2023-10-23

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