Journal
ACS NANO
Volume 11, Issue 11, Pages 11694-11700Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsnano.7b06871
Keywords
surface covalent organic frameworks; Kagome; scanning tunneling microscopy; monomer concentration; dynamic covalent bonds
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Funding
- National Natural Science Foundation of China [21433011, 91527303]
- Strategic Priority Research Program of the Chinese Academy of Sciences [XDB12020100]
- National Basic Research Program [2017YFA024702]
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Polymorphic single-layered covalent organic frameworks (sCOFs) via on-surface synthesis have been investigated by employing the tetradentate monomer 1,3,6,8-tetrakis(p-formylphenyl)pyrene with D-2h symmetry and ditopic linear diamine building blocks. Three kinds of well-ordered sCOFs, including rhombus, parallelogram, and Kagome networks, are observed on the graphite surface by scanning tunnel microscopy. The pore size and periodicity of sCOFs are tunable by employing diamine monomers with different lengths. Statistical analysis reveals that two types of quadrate networks are preferred at high concentration, whereas the occupancy of Kagome networks increases at low concentration. This trend can be understood by the differences in the network density of three kinds of networks. The reversibility and the self-sorting ability of the dynamic covalent reaction make it possible to control the polymorphic distribution similar to the principle demonstrated in supramolecular self-assembly.
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