Hernández-Toledo Hugo, Torrens Hugo, Flores-Álamo Marcos, De Cola Luisa, Moreno-Alcántar Guillermo
Facultad de Química, Universidad Nacional Autónoma de México Ciudad Universitaria, 04510 Cd., De Mx., Mexico.
Institut de Science et d'Ingénierie Supramoléculaires, Université de Strasbourg, 8 allée Gaspard Monge, 67000, Strasbourg, France.
Chemistry. 2021 Jun 4;27(32):8308-8314. doi: 10.1002/chem.202100865. Epub 2021 May 14.
Luminescent copper(I)-based compounds have recently attracted much attention since they can reach very high emission quantum yields. Interestingly, Cu(I) clusters can also be emissive, and the extension from small molecules to larger architecture could represent the first step towards novel materials that could be obtained by programming the units to undergo self-assembly. However, for Cu(I) compounds the formation of supramolecular systems is challenging due to the coordinative diversity of copper centers. This works shows that this diversity can be exploited in the construction of responsive systems. In detail, the changes in the emissive profile of different aggregates formed in water by phosphine-thioether copper(I) derivatives were followed. Our results demonstrate that the self-assembly and disassembly of Cu(I)-based coordination polymeric nanoparticles (CPNs) is sensitive to solvent composition. The solvent-induced changes are related to modifications in the coordination sphere of copper at the molecular level, which alters not only the emission profile but also the morphology of the aggregates. Our findings are expected to inspire the construction of smart supramolecular systems based on dynamic coordinative metal centers.
基于发光铜(I)的化合物最近备受关注,因为它们能够达到非常高的发射量子产率。有趣的是,铜(I)簇也可以发光,从小分子扩展到更大的结构可能是迈向新型材料的第一步,这些新型材料可以通过对单元进行编程使其进行自组装而获得。然而,对于铜(I)化合物,由于铜中心的配位多样性,超分子体系的形成具有挑战性。这项工作表明,这种多样性可用于构建响应体系。具体而言,跟踪了膦硫醚铜(I)衍生物在水中形成的不同聚集体发射谱的变化。我们的结果表明,基于铜(I)的配位聚合物纳米颗粒(CPN)的自组装和解组装对溶剂组成敏感。溶剂诱导的变化与分子水平上铜配位球的修饰有关,这不仅改变了发射谱,还改变了聚集体的形态。我们的发现有望激发基于动态配位金属中心的智能超分子体系的构建。