M<sub>12</sub>L<sub>24</sub> nanospheres as supramolecular templates for the controlled synthesis of Ir-nanoclusters and their use in the chemo-selective hydrogenation of nitro styrene

Metz, Lotte L.; Ham, Rens; Bobylev, Eduard O.; Brouwer, Kelly J. H.; van Blaaderen, Alfons; van de Poll, Rim C. J.; Drozhzhin, Victor R.; Hensen, Emiel J. M.; Reek, Joost N. H.

doi:10.1039/d4sc06324d

Chem. Sci.

2024

DOI: 10.1039/d4sc06324d

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

Lotte L. Metz,

Rens Ham,

Eduard O. Bobylev

et al.

Abstract: 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...

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Supramolecular Preorganization Rhodium and Iridium Metal Complexes Within M₁₂L₂₄ Self‐Assembled Nanospheres for the Confined Synthesis Rh/Ir Alloyed Nanoparticles

Metz,

Bobylev,

vandePoll

et al. 2024

ChemCatChem

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Controlling the size and composition of metal nanoparticles is of considerable interest, as these are essential to their catalytic properties. We report the controlled synthesis Rh nanoparticles by preorganisation of metal complexes inside Pt12L24 nanospheres based on complementary hydrogen bonds before the reduction step that leads to nanoparticle formation. The encapsulated RhI complexes (Rh‐s @ G‐sphere) led to reasonable size control (2.8 ± 0.9 nm). We also report the formation of Rh‐Ir alloyed nanoparticles with varying Rh/Ir compositions. These heterometallic particles were evaluated in the hydrogenation of cinnamaldehyde (7) as a probe reaction. Besides a high activity in this probe reaction, the Rh particles also catalyzed the conversion of the solvent (CH3CN). The formed basic amine leads to follow‐up reactions of the product and compatibility issues with the hosting nanosphere. The solvent hydrogenation was effectively suppressed by using the Rh:Ir alloyed nanoparticles, provided that they contain >66% Ir. The Rh:Ir alloyed nanoparticles displayed high catalytic activity, reaching optimal selectivity and activity at an 8:16 ‐ Rh:Ir ratio. The combined catalytic results illustrate that pre‐organisation of the metal complexes in the nanosphere before the reduction with hydrogen effectively facilitates the formation of Rh:Ir alloyed nanoparticles.

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Supramolecular Preorganization Rhodium and Iridium Metal Complexes Within M₁₂L₂₄ Self‐Assembled Nanospheres for the Confined Synthesis Rh/Ir Alloyed Nanoparticles

Metz,

Bobylev,

vandePoll

et al. 2024

ChemCatChem

View full text Add to dashboard Cite

show abstract

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

Abstract: 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...

Cited by 1 publication

References 68 publications

Supramolecular Preorganization Rhodium and Iridium Metal Complexes Within M₁₂L₂₄ Self‐Assembled Nanospheres for the Confined Synthesis Rh/Ir Alloyed Nanoparticles

Supramolecular Preorganization Rhodium and Iridium Metal Complexes Within M₁₂L₂₄ Self‐Assembled Nanospheres for the Confined Synthesis Rh/Ir Alloyed Nanoparticles

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

Abstract: 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...

Cited by 1 publication

References 68 publications

Supramolecular Preorganization Rhodium and Iridium Metal Complexes Within M12L24 Self‐Assembled Nanospheres for the Confined Synthesis Rh/Ir Alloyed Nanoparticles

Supramolecular Preorganization Rhodium and Iridium Metal Complexes Within M12L24 Self‐Assembled Nanospheres for the Confined Synthesis Rh/Ir Alloyed Nanoparticles

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Product

Resources

About

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

Supramolecular Preorganization Rhodium and Iridium Metal Complexes Within M₁₂L₂₄ Self‐Assembled Nanospheres for the Confined Synthesis Rh/Ir Alloyed Nanoparticles

Supramolecular Preorganization Rhodium and Iridium Metal Complexes Within M₁₂L₂₄ Self‐Assembled Nanospheres for the Confined Synthesis Rh/Ir Alloyed Nanoparticles