期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 61, 期 18, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202116980
关键词
Mechanochemistry; Metal-Coordination; Molecular Self-Assembly; Supramolecular Chemistry; Thermodynamic and Kinetic Products
资金
- ShanghaiTech University
- ShanghaiTech University [SPST-AIC10112914]
The study successfully synthesized the elusive cyclic dimer Pd2L2 for the first time using mechanochemical methods, and revealed the rapid conversion of Pd2L2 to Pd3L3 and Pd4L4 in solution as a kinetic process.
Pd-based molecular square Pd4L4 and triangle Pd3L3 represent the molecular ancestors of metal-coordination polyhedra that have been an integral part of the field for the last 30 years. Conventional solution-based reactions between cis-protected Pd ions and 2,2 '-bipyridine exclusively give Pd4L4 and/or Pd3L3 as the sole products. We herein show that, under solvent-free mechanochemical conditions, the self-assembly energy landscape can be thermodynamically manipulated to form an elusive cyclic dimer Pd2L2 for the first time. In the absence of solvent, Pd2L2 is indefinitely stable in the solid-state, but converts rapidly to its thermodynamic products Pd3L3 and Pd4L4 in solution, confirming Pd2L2 as a short-lived kinetic species in the solution-based self-assembly process. Our results highlight how mechanochemistry grants access to a vastly different chemical space than available under conventional solution conditions. This provides a unique opportunity to isolate elusive species in self-assembly processes that are too reactive to both see and capture.
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