Precise installation of photoredox/Ni dual-catalysts into MOF for enhancing photocatalytic cross-coupling

Constructing the dual-catalytic scaffolds with the pinpointed photoredox/organometallic sites is pivotal for metallaphotocatalysis, yet challenging. Herein, we demonstrate a versatile protocol of sequential dynamic assembly (SDA) for precise and quantitative installation of Ir-photoredox and Ni-cross-coupling catalysts into a robust metal-organic framework (MOF) to construct an Ir/Ni-catalyst LIFM-XYY-12. Remarkably, LIFM-XYY-12 presents excellent catalytic activity in photoredox-mediated Ni-catalysing cross-coupling reactions between various amines/thiols and aryl halides with yields up to 99%, especially for C–N coupling reaction, achieving fast catalytic reaction kinetics, which is nearly 20-fold than that of the homogeneous system, attributable to the installation of Ir III - and Ni II -sites in close proximity to effectively accelerate electron transfers from Ir- to Ni-centers. Moreover, high S -arylation chemoselectivity (⩾91%) is achieved for various aminothiols carrying primary and secondary arylamine groups, affording a variety of aminothioethers without resorting to protecting group chemistry. The underlying reaction mechanism has been detangled through comprehensive experiments and theoretical calculations. This work highlights SDA as a promising strategy to merge photoredox and transition-metal catalysis into MOF platform for a broad utility in organic transformations.