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Porous lanthanide metal–organic frameworks with metallic conductivity

Metallic charge transport and porosity appear almost mutually exclusive. Whereas metals demand large numbers of free carriers and must have minimal impurities and lattice vibrations to avoid charge scattering, the voids in porous materials limit the carrier concentration, provide ample space for imp...

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Autores principales: Skorupskii, Grigorii, Le, Khoa N., Cordova, Dmitri Leo Mesoza, Yang, Luming, Chen, Tianyang, Hendon, Christopher H., Arguilla, Maxx Q., Dincă, Mircea
Formato: Online Artículo Texto
Lenguaje:English
Publicado: National Academy of Sciences 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9407220/
https://www.ncbi.nlm.nih.gov/pubmed/35969747
http://dx.doi.org/10.1073/pnas.2205127119
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author Skorupskii, Grigorii
Le, Khoa N.
Cordova, Dmitri Leo Mesoza
Yang, Luming
Chen, Tianyang
Hendon, Christopher H.
Arguilla, Maxx Q.
Dincă, Mircea
author_facet Skorupskii, Grigorii
Le, Khoa N.
Cordova, Dmitri Leo Mesoza
Yang, Luming
Chen, Tianyang
Hendon, Christopher H.
Arguilla, Maxx Q.
Dincă, Mircea
author_sort Skorupskii, Grigorii
collection PubMed
description Metallic charge transport and porosity appear almost mutually exclusive. Whereas metals demand large numbers of free carriers and must have minimal impurities and lattice vibrations to avoid charge scattering, the voids in porous materials limit the carrier concentration, provide ample space for impurities, and create more charge-scattering vibrations due to the size and flexibility of the lattice. No microporous material has been conclusively shown to behave as a metal. Here, we demonstrate that single crystals of the porous metal–organic framework Ln(1.5)(2,3,6,7,10,11-hexaoxytriphenylene) (Ln = La, Nd) are metallic. The materials display the highest room-temperature conductivities of all porous materials, reaching values above 1,000 S/cm. Single crystals of the compounds additionally show clear temperature-deactivated charge transport, a hallmark of a metallic material. Lastly, a structural transition consistent with charge density wave ordering, present only in metals and rare in any materials, provides additional conclusive proof of the metallic nature of the materials. Our results provide an example of a metal with porosity intrinsic to its structure. We anticipate that the combination of porosity and chemical tunability that these materials possess will provide a unique handle toward controlling the unconventional states that lie within them, such as charge density waves that we observed, or perhaps superconductivity.
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spelling pubmed-94072202023-02-15 Porous lanthanide metal–organic frameworks with metallic conductivity Skorupskii, Grigorii Le, Khoa N. Cordova, Dmitri Leo Mesoza Yang, Luming Chen, Tianyang Hendon, Christopher H. Arguilla, Maxx Q. Dincă, Mircea Proc Natl Acad Sci U S A Physical Sciences Metallic charge transport and porosity appear almost mutually exclusive. Whereas metals demand large numbers of free carriers and must have minimal impurities and lattice vibrations to avoid charge scattering, the voids in porous materials limit the carrier concentration, provide ample space for impurities, and create more charge-scattering vibrations due to the size and flexibility of the lattice. No microporous material has been conclusively shown to behave as a metal. Here, we demonstrate that single crystals of the porous metal–organic framework Ln(1.5)(2,3,6,7,10,11-hexaoxytriphenylene) (Ln = La, Nd) are metallic. The materials display the highest room-temperature conductivities of all porous materials, reaching values above 1,000 S/cm. Single crystals of the compounds additionally show clear temperature-deactivated charge transport, a hallmark of a metallic material. Lastly, a structural transition consistent with charge density wave ordering, present only in metals and rare in any materials, provides additional conclusive proof of the metallic nature of the materials. Our results provide an example of a metal with porosity intrinsic to its structure. We anticipate that the combination of porosity and chemical tunability that these materials possess will provide a unique handle toward controlling the unconventional states that lie within them, such as charge density waves that we observed, or perhaps superconductivity. National Academy of Sciences 2022-08-15 2022-08-23 /pmc/articles/PMC9407220/ /pubmed/35969747 http://dx.doi.org/10.1073/pnas.2205127119 Text en Copyright © 2022 the Author(s). Published by PNAS. https://creativecommons.org/licenses/by-nc-nd/4.0/This article is distributed under Creative Commons Attribution-NonCommercial-NoDerivatives License 4.0 (CC BY-NC-ND) (https://creativecommons.org/licenses/by-nc-nd/4.0/) .
spellingShingle Physical Sciences
Skorupskii, Grigorii
Le, Khoa N.
Cordova, Dmitri Leo Mesoza
Yang, Luming
Chen, Tianyang
Hendon, Christopher H.
Arguilla, Maxx Q.
Dincă, Mircea
Porous lanthanide metal–organic frameworks with metallic conductivity
title Porous lanthanide metal–organic frameworks with metallic conductivity
title_full Porous lanthanide metal–organic frameworks with metallic conductivity
title_fullStr Porous lanthanide metal–organic frameworks with metallic conductivity
title_full_unstemmed Porous lanthanide metal–organic frameworks with metallic conductivity
title_short Porous lanthanide metal–organic frameworks with metallic conductivity
title_sort porous lanthanide metal–organic frameworks with metallic conductivity
topic Physical Sciences
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9407220/
https://www.ncbi.nlm.nih.gov/pubmed/35969747
http://dx.doi.org/10.1073/pnas.2205127119
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