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Abstract Due to their diverse potential in advanced electronics and energy technologies, electrically conducting metal‐organic frameworks (MOFs) are drawing significant attention. Although hexagonal 2D MOFs generally display impressive electrical conductivity because of their dual in‐plane (through bonds) and out‐of‐plane (through π‐stacked ligands) charge transport pathways, notable differences between these two orthogonal conduction routes cause anisotropic conductivity and lower bulk conductivity. To address this issue, we have developed the first redox‐complementary dual‐ligand 2D MOF Cu3(HHTP)(HHTQ), featuring a π‐donor hexahydroxytriphenylene (HHTP) ligand and a π‐acceptor hexahydroxytricycloquinazoline (HHTQ) ligand located at alternate corners of the hexagons, which form either parallel HHTP and HHTQ stacks (AA stacking) or alternating HHTP/HHTQ stacks (AB stacking) along the c‐axis. Regardless of the stacking pattern, Cu3(HHTP)(HHTQ) supports more effective out‐of‐plane conduction through either separate π‐donor and π‐acceptor stacks or alternating π‐donor/acceptor stacks, while promoting in‐plane conduction through the pushpull‐like heteroleptic coordination network. As a result, Cu3(HHTP)(HHTQ) exhibits higher bulk conductivity (0.12 S/m at 295 K) than single‐ligand MOFs Cu3(HHTP)2(7.3 × 10−2S/m) and Cu3(HHTQ)2(5.9 × 10−4S/m). This work introduces a new design approach to improve the bulk electrical conductivity of 2D MOFs by supporting charge transport in both in‐ and out‐of‐plane direcations.
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Electrically Conductive π‐Intercalated Graphitic Metal‐Organic Framework Containing Alternate π‐Donor/Acceptor Stacks
Abstract Two‐dimensional graphitic metal–organic frameworks (GMOF) often display impressive electrical conductivity chiefly due to efficient through‐bond in‐plane charge transport, however, less efficient out‐of‐plane conduction across the stacked layers creates large disparity between two orthogonal conduction pathways and dampens their bulk conductivity. To address this issue and engineer higher bulk conductivity in 2D GMOFs, we have constructed via an elegant bottom‐up method the first π‐intercalated GMOF (iGMOF1) featuring built‐in alternate π‐donor/acceptor (π‐D/A) stacks of CuII‐coordinated electron‐rich hexaaminotriphenylene (HATP) ligands and non‐coordinatively intercalated π‐acidic hexacyano‐triphenylene (HCTP) molecules, which facilitated out‐of‐plane charge transport while the hexagonal Cu3(HATP)2scaffold maintained in‐plane conduction. As a result, iGMOF1 attained an order of magnitude higher bulk electrical conductivity and much smaller activation energy than Cu3(HATP)2(σ=25 vs. 2 S m−1,Ea=36 vs. 65 meV), demostrating that simultaneous in‐plane (through‐bond) and out‐of‐plane (through πD/A stacks) charge transport can generate higher electrical conductivity in novel iGMOFs.
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- PAR ID:
- 10419164
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 62
- Issue:
- 26
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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