A stochastic model study on the self-assembly process of a Pd2L4 cage consisting of rigid ditopic ligands

The coordination self-assembly process of a Pd2L4 cage including rigid ditopic ligands, L, was studied numerically. A recently developed experimental approach (QASAP: quantitative analysis of self-assembly process) revealed that the rate-determining steps in the self-assembly of the Pd2L4 cage are i...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2019, Vol.21 (12), p.6341-6347
Main Authors: Takahashi, Satoshi, Sasaki, Yuya, Hiraoka, Shuichi, Sato, Hirofumi
Format: Article
Language:English
Subjects:
Cages
Exchanging
Ligands
Mathematical models
Parameters
Quantitative analysis
Rate constants
Self-assembly
Substrates
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Summary:The coordination self-assembly process of a Pd2L4 cage including rigid ditopic ligands, L, was studied numerically. A recently developed experimental approach (QASAP: quantitative analysis of self-assembly process) revealed that the rate-determining steps in the self-assembly of the Pd2L4 cage are intramolecular ligand exchanges at the late stages of the self-assembly. In this study, the self-assembly process before the rate-determining steps, which could not be investigated by experiment, was analyzed based on a minimal reaction network model. Only eight variable parameters of rate constants for ligand exchange reactions are sufficient enough to reproduce the time evolution of substrates and the products during the self-assembly of the cage. With these parameters, the major self-assembly pathway was determined. It was also found that a non-negligible amount of an incomplete cage (IC), Pd2L3X2 (X indicates the leaving ligand), which was not suggested by QASAP, should be transiently produced. Numerical tests also suggest that the small rate constant value of the intramolecular ligand exchanges due to a restricted geometry causes the final stage to seemingly become the rate-determining step.
ISSN:1463-9076
1463-9084
DOI:10.1039/c8cp06102e