Atomically precise single-crystal structures of electrically conducting 2D metal–organic frameworks
Electrically conducting 2D metal–organic frameworks (MOFs) have attracted considerable interest, as their hexagonal 2D lattices mimic graphite and other 2D van der Waals stacked materials. However, understanding their intrinsic properties remains a challenge because their crystals are too small or o...
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| Published in | Nature materials Vol. 20; no. 2; pp. 222 - 228 |
|---|---|
| Main Authors | , , , , , , , , , , , , , , , , , , , , |
| Format | Journal Article |
| Language | English |
| Published |
London
Nature Publishing Group UK
01.02.2021
Nature Publishing Group |
| Subjects | |
| Online Access | Get full text |
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| Abstract | Electrically conducting 2D metal–organic frameworks (MOFs) have attracted considerable interest, as their hexagonal 2D lattices mimic graphite and other 2D van der Waals stacked materials. However, understanding their intrinsic properties remains a challenge because their crystals are too small or of too poor quality for crystal structure determination. Here, we report atomically precise structures of a family of 2D
π
-conjugated MOFs derived from large single crystals of sizes up to 200 μm, allowing atomic-resolution analysis by a battery of high-resolution diffraction techniques. A designed ligand core rebalances the in-plane and out-of-plane interactions that define anisotropic crystal growth. We report two crystal structure types exhibiting analogous 2D honeycomb-like sheets but distinct packing modes and pore contents. Single-crystal electrical transport measurements distinctively demonstrate anisotropic transport normal and parallel to the
π
-conjugated sheets, revealing a clear correlation between absolute conductivity and the nature of the metal cation and 2D sheet packing motif.
Two-dimensional MOFs can possess porosity and electrical conductivity but are difficult to grow as single crystals. Here, by balancing in-plane and out-of-plane interactions, single crystals of sizes up to 200 µm are grown, allowing in-plane transport measurements and atomic-resolution analysis. |
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| AbstractList | Electrically conducting 2D metal-organic frameworks (MOFs) have attracted considerable interest, as their hexagonal 2D lattices mimic graphite and other 2D van der Waals stacked materials. However, understanding their intrinsic properties remains a challenge because their crystals are too small or of too poor quality for crystal structure determination. Here, we report atomically precise structures of a family of 2D π-conjugated MOFs derived from large single crystals of sizes up to 200 μm, allowing atomic-resolution analysis by a battery of high-resolution diffraction techniques. A designed ligand core rebalances the in-plane and out-of-plane interactions that define anisotropic crystal growth. We report two crystal structure types exhibiting analogous 2D honeycomb-like sheets but distinct packing modes and pore contents. Single-crystal electrical transport measurements distinctively demonstrate anisotropic transport normal and parallel to the π-conjugated sheets, revealing a clear correlation between absolute conductivity and the nature of the metal cation and 2D sheet packing motif.Electrically conducting 2D metal-organic frameworks (MOFs) have attracted considerable interest, as their hexagonal 2D lattices mimic graphite and other 2D van der Waals stacked materials. However, understanding their intrinsic properties remains a challenge because their crystals are too small or of too poor quality for crystal structure determination. Here, we report atomically precise structures of a family of 2D π-conjugated MOFs derived from large single crystals of sizes up to 200 μm, allowing atomic-resolution analysis by a battery of high-resolution diffraction techniques. A designed ligand core rebalances the in-plane and out-of-plane interactions that define anisotropic crystal growth. We report two crystal structure types exhibiting analogous 2D honeycomb-like sheets but distinct packing modes and pore contents. Single-crystal electrical transport measurements distinctively demonstrate anisotropic transport normal and parallel to the π-conjugated sheets, revealing a clear correlation between absolute conductivity and the nature of the metal cation and 2D sheet packing motif. Electrically conducting 2D metal-organic frameworks (MOFs) have attracted considerable interest, as their hexagonal 2D lattices mimic graphite and other 2D van der Waals stacked materials. However, understanding their intrinsic properties remains a challenge because their crystals are too small or of too poor quality for crystal structure determination. Here, we report atomically precise structures of a family of 2D pi-conjugated MOFs derived from large single crystals of sizes up to 200 mu m, allowing atomic-resolution analysis by a battery of high-resolution diffraction techniques. A designed ligand core rebalances the in-plane and out-of-plane interactions that define anisotropic crystal growth. We report two crystal structure types exhibiting analogous 2D honeycomb-like sheets but distinct packing modes and pore contents. Single-crystal electrical transport measurements distinctively demonstrate anisotropic transport normal and parallel to the pi-conjugated sheets, revealing a clear correlation between absolute conductivity and the nature of the metal cation and 2D sheet packing motif. Two-dimensional MOFs can possess porosity and electrical conductivity but are difficult to grow as single crystals. Here, by balancing in-plane and out-of-plane interactions, single crystals of sizes up to 200 mu m are grown, allowing in-plane transport measurements and atomic-resolution analysis. Electrically conducting 2D metal-organic frameworks (MOFs) have attracted considerable interest, as their hexagonal 2D lattices mimic graphite and other 2D van der Waals stacked materials. However, understanding their intrinsic properties remains a challenge because their crystals are too small or of too poor quality for crystal structure determination. Here, we report atomically precise structures of a family of 2D π-conjugated MOFs derived from large single crystals of sizes up to 200 μm, allowing atomic-resolution analysis by a battery of high-resolution diffraction techniques. A designed ligand core rebalances the in-plane and out-of-plane interactions that define anisotropic crystal growth. We report two crystal structure types exhibiting analogous 2D honeycomb-like sheets but distinct packing modes and pore contents. Single-crystal electrical transport measurements distinctively demonstrate anisotropic transport normal and parallel to the π-conjugated sheets, revealing a clear correlation between absolute conductivity and the nature of the metal cation and 2D sheet packing motif. Electrically conducting 2D metal–organic frameworks (MOFs) have attracted considerable interest, as their hexagonal 2D lattices mimic graphite and other 2D van der Waals stacked materials. However, understanding their intrinsic properties remains a challenge because their crystals are too small or of too poor quality for crystal structure determination. Here, we report atomically precise structures of a family of 2D π -conjugated MOFs derived from large single crystals of sizes up to 200 μm, allowing atomic-resolution analysis by a battery of high-resolution diffraction techniques. A designed ligand core rebalances the in-plane and out-of-plane interactions that define anisotropic crystal growth. We report two crystal structure types exhibiting analogous 2D honeycomb-like sheets but distinct packing modes and pore contents. Single-crystal electrical transport measurements distinctively demonstrate anisotropic transport normal and parallel to the π -conjugated sheets, revealing a clear correlation between absolute conductivity and the nature of the metal cation and 2D sheet packing motif. Two-dimensional MOFs can possess porosity and electrical conductivity but are difficult to grow as single crystals. Here, by balancing in-plane and out-of-plane interactions, single crystals of sizes up to 200 µm are grown, allowing in-plane transport measurements and atomic-resolution analysis. Electrically conducting 2D metal–organic frameworks (MOFs) have attracted considerable interest, as their hexagonal 2D lattices mimic graphite and other 2D van der Waals stacked materials. However, understanding their intrinsic properties remains a challenge because their crystals are too small or of too poor quality for crystal structure determination. Here, we report atomically precise structures of a family of 2D π-conjugated MOFs derived from large single crystals of sizes up to 200 μm, allowing atomic-resolution analysis by a battery of high-resolution diffraction techniques. A designed ligand core rebalances the in-plane and out-of-plane interactions that define anisotropic crystal growth. We report two crystal structure types exhibiting analogous 2D honeycomb-like sheets but distinct packing modes and pore contents. Single-crystal electrical transport measurements distinctively demonstrate anisotropic transport normal and parallel to the π-conjugated sheets, revealing a clear correlation between absolute conductivity and the nature of the metal cation and 2D sheet packing motif.Two-dimensional MOFs can possess porosity and electrical conductivity but are difficult to grow as single crystals. Here, by balancing in-plane and out-of-plane interactions, single crystals of sizes up to 200 µm are grown, allowing in-plane transport measurements and atomic-resolution analysis. |
| Author | Yang, Luming Arguilla, Maxx Q. Kong, Jing Hendon, Christopher H. Chen, Tianyang Sun, Chenyue Dincă, Mircea Yang, Min Chieh Skorupskii, Grigorii Zhang, Weizhe Dip, Phat Vinh Miller, Jeffrey T. Parent, Lucas R. Dou, Jin-Hu Mancuso, Jenna L. Libretto, Nicole J. Luo, Yi Sun, Lei Sun, Junliang Li, Jian Brignole, Edward J. |
| Author_xml | – sequence: 1 givenname: Jin-Hu orcidid: 0000-0002-6920-9051 surname: Dou fullname: Dou, Jin-Hu organization: Department of Chemistry, Massachusetts Institute of Technology – sequence: 2 givenname: Maxx Q. surname: Arguilla fullname: Arguilla, Maxx Q. organization: Department of Chemistry, Massachusetts Institute of Technology – sequence: 3 givenname: Yi surname: Luo fullname: Luo, Yi organization: College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, Department of Materials and Environmental Chemistry, Stockholm University – sequence: 4 givenname: Jian surname: Li fullname: Li, Jian organization: College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, Department of Materials and Environmental Chemistry, Stockholm University – sequence: 5 givenname: Weizhe surname: Zhang fullname: Zhang, Weizhe organization: National Facility for Protein Science, Shanghai Advanced Research Institute – sequence: 6 givenname: Lei surname: Sun fullname: Sun, Lei organization: Department of Chemistry, Massachusetts Institute of Technology – sequence: 7 givenname: Jenna L. surname: Mancuso fullname: Mancuso, Jenna L. organization: Material Science Institute, Department of Chemistry and Biochemistry, University of Oregon – sequence: 8 givenname: Luming surname: Yang fullname: Yang, Luming organization: Department of Chemistry, Massachusetts Institute of Technology – sequence: 9 givenname: Tianyang surname: Chen fullname: Chen, Tianyang organization: Department of Chemistry, Massachusetts Institute of Technology – sequence: 10 givenname: Lucas R. surname: Parent fullname: Parent, Lucas R. organization: University of Connecticut, Innovation Partnership Building, University of Connecticut – sequence: 11 givenname: Grigorii surname: Skorupskii fullname: Skorupskii, Grigorii organization: Department of Chemistry, Massachusetts Institute of Technology – sequence: 12 givenname: Nicole J. orcidid: 0000-0002-6922-2790 surname: Libretto fullname: Libretto, Nicole J. organization: Davidson School of Chemical Engineering, Purdue University – sequence: 13 givenname: Chenyue orcidid: 0000-0002-7524-5323 surname: Sun fullname: Sun, Chenyue organization: Department of Chemistry, Massachusetts Institute of Technology – sequence: 14 givenname: Min Chieh surname: Yang fullname: Yang, Min Chieh organization: Material Science Institute, Department of Chemistry and Biochemistry, University of Oregon – sequence: 15 givenname: Phat Vinh orcidid: 0000-0002-1535-9644 surname: Dip fullname: Dip, Phat Vinh organization: Department of Biology, Massachusetts Institute of Technology – sequence: 16 givenname: Edward J. surname: Brignole fullname: Brignole, Edward J. organization: Department of Biology, Massachusetts Institute of Technology – sequence: 17 givenname: Jeffrey T. surname: Miller fullname: Miller, Jeffrey T. organization: Davidson School of Chemical Engineering, Purdue University – sequence: 18 givenname: Jing surname: Kong fullname: Kong, Jing organization: Department of Electrical and Engineering and Computer Science, Massachusetts Institute of Technology – sequence: 19 givenname: Christopher H. orcidid: 0000-0002-7132-768X surname: Hendon fullname: Hendon, Christopher H. organization: Material Science Institute, Department of Chemistry and Biochemistry, University of Oregon – sequence: 20 givenname: Junliang orcidid: 0000-0003-4074-0962 surname: Sun fullname: Sun, Junliang email: junliang.sun@pku.edu.cn organization: College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, Department of Materials and Environmental Chemistry, Stockholm University – sequence: 21 givenname: Mircea orcidid: 0000-0002-1262-1264 surname: Dincă fullname: Dincă, Mircea email: mdinca@mit.edu organization: Department of Chemistry, Massachusetts Institute of Technology |
| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/33230325$$D View this record in MEDLINE/PubMed https://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-189356$$DView record from Swedish Publication Index |
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| Snippet | Electrically conducting 2D metal–organic frameworks (MOFs) have attracted considerable interest, as their hexagonal 2D lattices mimic graphite and other 2D van... Electrically conducting 2D metal-organic frameworks (MOFs) have attracted considerable interest, as their hexagonal 2D lattices mimic graphite and other 2D van... |
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| SubjectTerms | 119/118 140/131 142/126 639/301/299/1013 639/638/263/915 639/638/298/921 Biomaterials Chemistry and Materials Science Condensed Matter Physics Crystal growth Crystal structure Crystals Electrical resistivity Lattices Materials Science Metal-organic frameworks Nanotechnology Optical and Electronic Materials Porosity Sheets Single crystals |
| Title | Atomically precise single-crystal structures of electrically conducting 2D metal–organic frameworks |
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