Biasing the Formation of Solution‐Unstable Intermediates in Coordination Self‐Assembly by Mechanochemistry

Due to the reversible nature of coordination bonds and solvation effect, coordination self‐assembly pathways are often difficult to elucidate experimentally in solution, as intermediates and products are in constant equilibration. The present study shows that some of these transient and high‐energy...

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Bibliographic Details
Published in:Chemistry : a European journal 2023-12, Vol.29 (67), p.e202302563-n/a
Main Authors: Liu, Yan, Liu, Fang‐Zi, Li, Shi, Liu, Hua, Yan, KaKing
Format: Article
Language:English
Subjects:
ball mill
Ball milling
Benzene
Cages
Chemistry
Coordination
Intermediates
Magnetic resonance spectroscopy
mechanochemistry
metal-coordination
NMR
NMR spectroscopy
Nuclear magnetic resonance
Self-assembly
Solvation
supramolecular chemistry
Triazine
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Summary:Due to the reversible nature of coordination bonds and solvation effect, coordination self‐assembly pathways are often difficult to elucidate experimentally in solution, as intermediates and products are in constant equilibration. The present study shows that some of these transient and high‐energy self‐assembly intermediates can be accessed by means of ball‐milling approaches. Among them, highly aqueous‐unstable Pd3L11 and Pd6L14 open‐cage intermediates of the framed Fujita Pd6L14 cage and Pd2L22, Pd3L21 and Pd4L22 intermediates of Mukherjee Pd6L24 capsule are successfully trapped in solid‐state, where Pd=tmedaPd2+, L1=2,4,6‐tris(4‐pyridyl)‐1,3,5‐triazine and L2=1,3,5‐tris(1‐imidazolyl)benzene). Their structures are assigned by a combination of solution‐based characterization tools such as standard NMR spectroscopy, DOSY NMR, ESI‐MS and X‐ray diffraction. Collectively, these results highlight the opportunity of using mechanochemistry to access unique chemical space with vastly different reactivity compared to conventional solution‐based supramolecular self‐assembly reactions. A solvent‐free ball‐mill approach is developed to modulate coordination self‐assembly energy landscapes, allowing access to self‐assembly intermediates in the solid state that are too short‐lived to be observed in traditional solution‐based approaches.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202302563