The Role of a Confined Space on the Reactivity and Emission Properties of Copper(I) Clusters.

Metal clusters have gained a lot of interest for their remarkable photoluminescence and catalytic properties. However, a major drawback of such materials is their poor stability in air and humidity conditions. Herein we describe a versatile method to synthesize luminescent Cu(I) clusters inside the pores of zeolites, using a sublimation technique with the help of high vacuum and high temperature. The porous materials play an essential role as a protecting media against the undesirable and easy oxidation of Cu(I). The obtained clusters show fascinating luminescence properties, and their reactivity can be triggered by insertion in the pores of organic monodentate ligands such as pyridine or triphenylphosphine. The coordinating ligands can lead to the formation of Cu(I) complexes with completely different emission properties. In the case of pyridine, the final compound was characterized and identified as a cubane-like structure. A thermochromism effect is also observed, featuring, for instance, a hypsochromic effect for a phosphine derivative at 77K. The stability of the encapsulated systems in zeolites is rather enthralling: they are stable and emissive even after several months in the air.