M₁₂L₂₄ nanospheres as supramolecular templates for the controlled synthesis of Ir-nanoclusters and their use in the chemo-selective hydrogenation of nitro styrene

Controlled preparation of ultrafine metal nanoclusters (<2 nm) is challenging, yet important as the properties of these clusters are inherently linked to their size and local microenvironment. In the present work, we report the utilization of supramolecular pre-organization of organometallic complexes within well-defined M₁₂L₂₄ coordination spheres for the controlled synthesis of ultrafine Ir nanoclusters by reduction with molecular hydrogen. For this purpose, 24 sulfonate functionalized N-heterocyclic carbene (NHC) Ir complexes (Ir-s) were bound within a well-defined M₁₂L₂₄ nanosphere that is equipped with 24 guanidinium binding sites (G-sphere). Reduction of these pre-organized metal complexes by hydrogenation led to the templated formation of nanoclusters with a narrow size distribution (1.8 ± 0.4 nm in diameter). It was demonstrated through ¹H-DOSY-NMR and HAADF-STEM-EDX experiments that the resulting nanoclusters reside within the nanospheres. The reduction of similar non-encapsulated metal complexes in the presence of nanosphere systems (Ir-s + M-sphere or Ir-p + G-sphere) resulted in larger particles with a broader size distribution (2.3 ± 2.1 nm and 6.6 ± 3.2 nm for Ir-s + M-sphere and Ir-p + G-sphere respectively). The encapsulated nanoclusters were used as a homogeneous catalyst in the selective hydrogenation of 4-nitrostyrene to 4-ethylnitrobenzene and display absolute selectivity, which is even maintained at full conversions, whereas the larger non-encapsulated clusters were less selective as these also showed reduction of the nitro functionality.