Mechanism for Topology Selection of Isomeric Two-Dimensional Covalent Organic Frameworks.
J Phys Chem Lett
; 13(30): 7087-7093, 2022 Aug 04.
Article
in En
| MEDLINE
| ID: mdl-35900203
ABSTRACT
The mechanism of growth of one of the competitive topologies for covalent organic frameworks with constitutional isomers is poorly understood. Herein, we employ molecular dynamics to study the isoenergetic assembly of the rhombic square (sql) and Kagome lattice (kgm). The concentration, solvent conditions, and the reversibility of chemical reactions are considered by means of an Arrhenius two-state model to describe the reactions. High concentrations and poor solvent both result in sql, agreeing well with recent experiments. Moreover, the high reversibility of reactions gives rise to sql, while the low reversibility leads to kgm, suggesting a new way of regulating the topology. Our analyses support that the nucleation of isomers influenced by experimental conditions is responsible for the selection of topologies, which improves understanding of the control of topology. We also propose a strategy in which a two-step growth can be exploited to greatly improve the crystallinity of kgm.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
J Phys Chem Lett
Year:
2022
Document type:
Article
Affiliation country:
China