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Updated: Nov 2, 2025
Ligand-Mediated Nucleation and Growth of Palladium Metal Nanoparticles
Published on: June 25, 2018
Topological prediction of palladium coordination cages
David A Poole1, Eduard O Bobylev1, Simon Mathew1
1Homogeneous, Supramolecular, and Bio-inspired Catalysis Group, van't Hoff Institute for Molecular Science (HIMS), University of Amsterdam (UvA) Science Park 904 1098 XH Amsterdam The Netherlands j.n.h.reek@uva.nl.
Abstract:
The preparation of functionalized, heteroleptic Pd L2 coordination cages is desirable for catalytic and optoelectronic applications. Current rational design of these cages uses the angle between metal-binding (∠B) sites of the di(pyridyl)arene linker to predict the topology of homoleptic cages obtained via non-covalent chemistry. However, this model neglects the contributions of steric bulk between the pyridyl residues-a prerequisite for endohedrally functionalized cages, and fails to rationalize heteroleptic cages. We describe a classical mechanics (CM) approach to predict the topological outcomes of Pd L2 coordination cage formation with arbitrary linker combinations, accounting for the electronic effects of coordination and steric effects of linker structure. Initial validation of our CM method with reported homoleptic Pd12 LFu 24 (LFu = 2,5-bis(pyridyl)furan) assembly suggested the formation of a minor topology Pd15 LFu 30, identified experimentally by mass spectrometry. Application to heteroleptic cage systems employing mixtures of LFu (∠B = 127°) and its thiophene congener LTh (∠B = 149° ∠B exp = 152.4°) enabled prediction of Pd12L24 and Pd24L48 coordination cages formation, reliably emulating experimental data. Finally, the topological outcome for exohedrally (LEx) and endohedrally (LEn) functionalized heteroleptic Pd L2 coordination cages were predicted to assess the effect of steric bulk on both topological outcomes and coordination cage yields, with comparisons drawn to experimental data.
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