Angew. Chem. Int. Ed. (2023) by CMM

Stable Luminescent [Cu(NN)(PP)]+ Complexes Incorporating a β-Cyclodextrin-Based Diphosphane Ligand with Metal-Confining Properties
Dr. Tuan-Anh Phan, Dr. Nicola Armaroli, Dr. Alejandra Saavedra Moncada, Dr. Elisa Bandini, Dr. Béatrice Delavaux-Nicot, Dr. Jean-François Nierengarten, Prof. Dominique Armspach
Angew. Chem. Int. Ed., 202362, e202214638


A β-cyclodextrin-based diphosphane with metal-confining properties was efficiently synthesized thanks to an unprecedented Smiles-like rearrangement of diphenyl-(2-phosphanylphenyl)phosphane in the presence of excess n-BuLi. The cis-chelating bidentate ligand is capable of forming very stable heteroleptic [Cu(NN)(PP)]+ complexes in which a metal-bound diimine ligand (bpy, phen, or mmp) is located within the cyclodextrin cavity. As a result of ligand encapsulation, flattening of the metal tetrahedral geometry in the excited state is disfavored, thereby resulting in enhanced luminescent properties.