Huitorel Brendan, El Moll Hani, Utrera-Melero Raquel, Cordier Marie, Fargues Alexandre, Garcia Alain, Massuyeau Florian, Martineau-Corcos Charlotte, Fayon Franck, Rakhmatullin Aydar, Kahlal Samia, Saillard Jean-Yves, Gacoin Thierry, Perruchas Sandrine
Laboratoire de Physique de la Matière Condensée (PMC) , CNRS-Ecole Polytechnique , 91128 Palaiseau Cedex, France.
Institut des Matériaux Jean Rouxel (IMN) , Université de Nantes, CNRS , 2 rue de la Houssinière , BP 32229, 44322 Nantes cedex 3, France.
Inorg Chem. 2018 Apr 16;57(8):4328-4339. doi: 10.1021/acs.inorgchem.7b03160. Epub 2018 Apr 5.
Luminescent materials based on copper complexes are currently receiving increasing attention because of their rich photophysical properties, opening a wide field of applications. The copper iodide clusters formulated [CuIL] (L = ligand), are particularly relevant for the development of multifunctional materials based on their luminescence stimuli-responsive properties. In this context, controlling and modulating their photophysical properties is crucial and this can only be achieved by thorough understanding of the origin of the optical properties. We thus report here, the comparative study of a series of cubane copper iodide clusters coordinated by different phosphine ligands, with the goal of analyzing the effect of the ligands nature on the photoluminescence properties. The synthesis, structural, and photophysical characterizations along with theoretical investigations of copper iodide clusters with ligands presenting different electronic properties, are described. A method to simplify the analysis of the P solid-state NMR spectra is also reported. While clusters with electron-donating groups present classical luminescence properties, the cluster bearing strong electron-withdrawing substituents exhibits original behavior demonstrating a clear influence of the ligands properties. In particular, the electron-withdrawing character induces a decrease in energy of the unoccupied molecular orbitals, that consequently impacts the emission properties. The modification of the luminescence thermochromic properties of the clusters are supported by density functional theory (DFT) calculations. This study demonstrates that the control of the luminescence properties of these compounds can be achieved through modification of the coordinated ligands, nevertheless the role of the crystal packing should not be underestimated.
基于铜配合物的发光材料因其丰富的光物理性质目前正受到越来越多的关注，从而开辟了广阔的应用领域。化学式为[CuIL]（L = 配体）的碘化铜簇合物，基于其发光刺激响应特性，对于多功能材料的开发尤为重要。在此背景下，控制和调节它们的光物理性质至关重要，而这只能通过深入了解光学性质的起源来实现。因此，我们在此报告了一系列由不同膦配体配位的立方烷碘化铜簇合物的对比研究，目的是分析配体性质对光致发光性质的影响。描述了具有不同电子性质配体的碘化铜簇合物的合成、结构和光物理表征以及理论研究。还报道了一种简化固态磷核磁共振谱分析的方法。虽然带有供电子基团的簇合物具有典型的发光性质，但带有强吸电子取代基的簇合物表现出独特的行为，表明配体性质有明显影响。特别是，吸电子特性导致未占据分子轨道能量降低，从而影响发射性质。密度泛函理论（DFT）计算支持了簇合物发光热致变色性质的改变。这项研究表明，通过修饰配位配体可以实现对这些化合物发光性质的控制，不过晶体堆积的作用也不应被低估。
