Mesoporous Mixed-Metal-Organic Framework Incorporating a [Ru(Phen)3]2+ Photosensitizer for Highly Efficient Aerobic Photocatalytic Oxidative Coupling of Amines

[Ru(Phen)(3)](2+) (phen = phenanthroline)asa very classical photosensitizer possesses strong absorption in thevisible range and facilitates photoinduced electron transfer, whichplays a vital role in regulating photochemical reactions. However,it remains a significant challenge to utilize more adequately andexploit more efficiently the ruthenium-based materials due to theuniqueness, scarcity, and nonrenewal of the noble metal. Here, weintegrate the intrinsic advantages of the ruthenium-based photosensitizerand mesoporous metal-organic frameworks (meso-MOFs) into a[Ru(Phen)(3)](2+) photosensitizer-embedded heterometallicNi(II)/Ru(II) meso-MOF (LTG-NiRu) via the metalloligandapproach. LTG-NiRu, with an extremely robust frameworkand a large one-dimensional (1D) channel, not only makes rutheniumphotosensitizer units anchored in the inner wall of meso-MOF tubesto circumvent the problem of product/catalyst separation and recyclingof catalysts in heterogeneous systems but also exhibits exceptionalactivities for the aerobic photocatalytic oxidative coupling of aminederivatives as a general photocatalyst. The conversion of the light-inducedoxidative coupling reaction for various benzylamines is similar to 100%in 1 h, and more than 20 chemical products generated by photocatalyticoxidative cycloaddition of N-substituted maleimides and N,N-dimethylaniline can be synthesized easily inthe presence of LTG-NiRu upon visible light irradiation.Moreover, recycling experiments demonstrate that LTG-NiRu is an excellent heterogeneous photocatalyst with high stabilityand excellent reusability. LTG-NiRu represents a greatpotential photosensitizer-based meso-MOF platform with an efficientaerobic photocatalytic oxidation function that is convenient for gram-scalesynthesis.