Tunable Crystallinity and Electron Conduction in Wavy 2D Conjugated Metal-Organic Frameworks via Halogen Substitution.
Small
; : e2306732, 2023 Dec 11.
Article
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| MEDLINE
| ID: mdl-38073322
ABSTRACT
Currently, most reported 2D conjugated metal-organic frameworks (2D c-MOFs) are based on planar polycyclic aromatic hydrocarbons (PAHs) with symmetrical functional groups, limiting the possibility of introducing additional substituents to fine-tune the crystallinity and electrical properties. Herein, a novel class of wavy 2D c-MOFs with highly substituted, core-twisted hexahydroxy-hexa-cata-benzocoronenes (HH-cHBCs) as ligands is reported. By tailoring the substitution of the c-HBC ligands with electron-withdrawing groups (EWGs), such as fluorine, chlorine, and bromine, it is demonstrated that the crystallinity and electrical conductivity at the molecular level can be tuned. The theoretical calculations demonstrate that F-substitution leads to a more reversible coordination bonding between HH-cHBCs and copper metal center, due to smaller atomic size and stronger electron-withdrawing effect. As a result, the achieved F-substituted 2D c-MOF exhibits superior crystallinity, comprising ribbon-like single crystals up to tens of micrometers in length. Moreover, the F-substituted 2D c-MOF displays higher electrical conductivity (two orders of magnitude) and higher charge carrier mobility (almost three times) than the Cl-substituted one. This work provides a new molecular design strategy for the development of wavy 2D c-MOFs and opens a new route for tailoring the coordination reversibility by ligand substitution toward increased crystallinity and superior electric conductivity.
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1
Colección:
01-internacional
Banco de datos:
MEDLINE
Idioma:
En
Revista:
Small
Asunto de la revista:
ENGENHARIA BIOMEDICA
Año:
2023
Tipo del documento:
Article
País de afiliación:
Alemania