A zero-valent palladium cluster-organic framework

Acquiring spatial control of nanoscopic metal clusters is central to their function as efficient multi-electron catalysts. However, dispersing metal clusters on surfaces or in porous hosts is accompanied by an intrinsic heterogeneity that hampers detailed understanding of the chemical structure and its relation to reactivities. Tethering pre-assembled molecular metal clusters into polymeric, crystalline 2D or 3D networks constitutes an unproven approach to realizing ordered arrays of chemically well-defined metal clusters. Herein, we report the facile synthesis of a {Pd₃} cluster-based organometallic framework from a molecular triangulo-Pd₃(CNXyl)₆ (Xyl = xylyl; Pd₃) cluster under chemically mild conditions. The formally zero-valent Pd₃ cluster readily engages in a complete ligand exchange when exposed to a similar, ditopic isocyanide ligand, resulting in polymerization into a 2D coordination network (Pd₃-MOF). The structure of Pd₃-MOF could be unambiguously determined by continuous rotation 3D electron diffraction (3D-ED) experiments to a resolution of ~1.0 Å (>99% completeness), showcasing the applicability of 3D-ED to nanocrystalline, organometallic polymers. Pd₃-MOF displays Pd⁰₃ cluster nodes, which possess significant thermal and aerobic stability, and activity towards hydrogenation catalysis. Importantly, the realization of Pd₃-MOF paves the way for the exploitation of metal clusters as building blocks for rigidly interlocked metal nanoparticles at the molecular limit.