Back to Search
Start Over
Tunable Crystallinity and Electron Conduction in Wavy 2D Conjugated Metal-Organic Frameworks via Halogen Substitution.
- Source :
-
Small (Weinheim an der Bergstrasse, Germany) [Small] 2024 Apr; Vol. 20 (17), pp. e2306732. Date of Electronic Publication: 2023 Dec 11. - Publication Year :
- 2024
-
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.<br /> (© 2023 The Authors. Small published by Wiley‐VCH GmbH.)
Details
- Language :
- English
- ISSN :
- 1613-6829
- Volume :
- 20
- Issue :
- 17
- Database :
- MEDLINE
- Journal :
- Small (Weinheim an der Bergstrasse, Germany)
- Publication Type :
- Academic Journal
- Accession number :
- 38073322
- Full Text :
- https://doi.org/10.1002/smll.202306732