Metal-organic framework composites with luminescent gold(iii) complexes. Strongly emissive and long-lived excited states in open air and photo-catalysis.

Abstract

The encapsulation of luminescent gold(iii) complexes by metal-organic frameworks (MOFs) lays the groundwork for new phosphorescent materials with activities that are not readily achieved by the host MOF materials or gold(iii) complexes alone. In this work, strong phosphorescence with lifetimes of up to ∼50 μs in open air at room temperature has been achieved by incorporation of cationic cyclometalated gold(iii) complexes into MOFs with anionic frameworks to form AuIII@MOFs. The AuIII@MOFs display solid state two-photon-induced phosphorescence. Photo-reduction of methyl viologen to the reduced radical was achieved inside AuIII@MOFs and in the presence of Et3N upon excitation at λ > 370 nm under ambient conditions. These AuIII@MOFs comprise a class of reusable and size-selective heterogeneous photo-catalysts for the aerobic oxidation of secondary amines to imines as well as five other reactions, including oxidative C-H functionalization under aerobic conditions.