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Title: Guest-induced emergent properties in Metal–Organic Frameworks

Abstract

Metal–Organic frameworks (MOFs) are crystalline nanoporous materials comprised of organic electron donors linked to metal ions by strong coordination bonds. Applications such as gas storage and separations are currently receiving considerable attention, but if the unique properties of MOFs could be extended to electronics, magnetics, and photonics, the impact on material science would greatly increase. Recently, we obtained “emergent properties,” such as electronic conductivity and energy transfer, by infiltrating MOF pores with “guest” molecules that interact with the framework electronic structure. In this Perspective, we define a path to emergent properties based on the Guest@MOF concept, using zinc-carboxylate and copper-paddlewheel MOFs for illustration. Energy transfer and light harvesting are discussed for zinc carboxylate frameworks infiltrated with triplet-scavenging organometallic compounds and thiophene- and fullerene-infiltrated MOF-177. In addition, we discuss the mechanism of charge transport in TCNQ-infiltrated HKUST-1, the first MOF with electrical conductivity approaching conducting organic polymers. Lastly, these examples show that guest molecules in MOF pores should be considered not merely as impurities or analytes to be sensed but also as an important aspect of rational design.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [2];  [2];  [1];  [2]
  1. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  2. Stanford Univ., Stanford, CA (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Renewable Power Office. Solar Energy Technologies Office
OSTI Identifier:
1235927
Report Number(s):
SAND-2015-20820J
Journal ID: ISSN 1948-7185; 558248
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 6; Journal Issue: 7; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Allendorf, Mark D., Foster, Michael E., Léonard, François, Stavila, Vitalie, Feng, Patrick L., Doty, F. Patrick, Leong, Kirsty, Ma, Eric Yue, Johnston, Scott R., Talin, A. Alec, and Shen, Zhi -Xun. Guest-induced emergent properties in Metal–Organic Frameworks. United States: N. p., 2015. Web. doi:10.1021/jz5026883.
Allendorf, Mark D., Foster, Michael E., Léonard, François, Stavila, Vitalie, Feng, Patrick L., Doty, F. Patrick, Leong, Kirsty, Ma, Eric Yue, Johnston, Scott R., Talin, A. Alec, & Shen, Zhi -Xun. Guest-induced emergent properties in Metal–Organic Frameworks. United States. doi:10.1021/jz5026883.
Allendorf, Mark D., Foster, Michael E., Léonard, François, Stavila, Vitalie, Feng, Patrick L., Doty, F. Patrick, Leong, Kirsty, Ma, Eric Yue, Johnston, Scott R., Talin, A. Alec, and Shen, Zhi -Xun. Thu . "Guest-induced emergent properties in Metal–Organic Frameworks". United States. doi:10.1021/jz5026883. https://www.osti.gov/servlets/purl/1235927.
@article{osti_1235927,
title = {Guest-induced emergent properties in Metal–Organic Frameworks},
author = {Allendorf, Mark D. and Foster, Michael E. and Léonard, François and Stavila, Vitalie and Feng, Patrick L. and Doty, F. Patrick and Leong, Kirsty and Ma, Eric Yue and Johnston, Scott R. and Talin, A. Alec and Shen, Zhi -Xun},
abstractNote = {Metal–Organic frameworks (MOFs) are crystalline nanoporous materials comprised of organic electron donors linked to metal ions by strong coordination bonds. Applications such as gas storage and separations are currently receiving considerable attention, but if the unique properties of MOFs could be extended to electronics, magnetics, and photonics, the impact on material science would greatly increase. Recently, we obtained “emergent properties,” such as electronic conductivity and energy transfer, by infiltrating MOF pores with “guest” molecules that interact with the framework electronic structure. In this Perspective, we define a path to emergent properties based on the Guest@MOF concept, using zinc-carboxylate and copper-paddlewheel MOFs for illustration. Energy transfer and light harvesting are discussed for zinc carboxylate frameworks infiltrated with triplet-scavenging organometallic compounds and thiophene- and fullerene-infiltrated MOF-177. In addition, we discuss the mechanism of charge transport in TCNQ-infiltrated HKUST-1, the first MOF with electrical conductivity approaching conducting organic polymers. Lastly, these examples show that guest molecules in MOF pores should be considered not merely as impurities or analytes to be sensed but also as an important aspect of rational design.},
doi = {10.1021/jz5026883},
journal = {Journal of Physical Chemistry Letters},
number = 7,
volume = 6,
place = {United States},
year = {2015},
month = {3}
}

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Works referencing / citing this record:

Semiconducting Coordination Polymers Based on the Predesigned Ternary Te-Fe-Cu Carbonyl Cluster and Conjugation-Interrupted Dipyridyl Linkers
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  • Chemistry - A European Journal, Vol. 23, Issue 47
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Electrical semiconduction modulated by light in a cobalt and naphthalene diimide metal-organic framework
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  • Castaldelli, Evandro; Imalka Jayawardena, K. D. G.; Cox, David C.
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/s41467-017-02215-7

Application of a novel 2D cadmium( ii )-MOF in the formation of a photo-switch with a substantial on–off ratio
journal, January 2015

  • Roy, Sumit; Dey, Arka; Ray, Partha Pratim
  • Chemical Communications, Vol. 51, Issue 65
  • DOI: 10.1039/c5cc04323a

Water-triggered macroscopic structural transformation of a metal–organic framework
journal, January 2016

  • Ohtani, Masataka; Takase, Kazutaka; Wang, Pengyu
  • CrystEngComm, Vol. 18, Issue 11
  • DOI: 10.1039/c6ce00031b

A highly emissive and stable zinc( ii ) metal–organic framework as a host–guest chemopalette for approaching white-light-emission
journal, January 2017

  • Cai, Hong; Xu, Li-Li; Lai, He-Yun
  • Chemical Communications, Vol. 53, Issue 56
  • DOI: 10.1039/c7cc03350h

Redox-active metal–organic frameworks for energy conversion and storage
journal, January 2019

  • Calbo, Joaquín; Golomb, Matthias J.; Walsh, Aron
  • Journal of Materials Chemistry A, Vol. 7, Issue 28
  • DOI: 10.1039/c9ta04680a

Crystal structure of bis[tris(1,10-phenanthroline-κ 2 N , N ′)cobalt(II)] tetranitrate N , N ′-(1,4-phenylenedicarbonyl)diglycine solvate octahydrate
journal, July 2015

  • Pook, Niels-Patrick; Hentrich, Philipp; Gjikaj, Mimoza
  • Acta Crystallographica Section E Crystallographic Communications, Vol. 71, Issue 8
  • DOI: 10.1107/s2056989015013006

Schalten in Metall‐organischen Gerüsten
journal, December 2019


Electrically Conducting Nanocomposites of Carbon Nanotubes and Metal‐Organic Frameworks with Strong Interactions between the two Components
journal, July 2019

  • Schulze, Hendrik A.; Hoppe, Bastian; Schäfer, Malte
  • ChemNanoMat, Vol. 5, Issue 9
  • DOI: 10.1002/cnma.201900110

Schalten in Metall‐organischen Gerüsten
journal, December 2019


Semiconducting Coordination Polymers Based on the Predesigned Ternary Te-Fe-Cu Carbonyl Cluster and Conjugation-Interrupted Dipyridyl Linkers
journal, June 2017

  • Shieh, Minghuey; Yu, Chia-Chi; Miu, Chia-Yeh
  • Chemistry - A European Journal, Vol. 23, Issue 47
  • DOI: 10.1002/chem.201701257

Electrically Conducting Nanocomposites of Carbon Nanotubes and Metal‐Organic Frameworks with Strong Interactions between the two Components
journal, July 2019

  • Schulze, Hendrik A.; Hoppe, Bastian; Schäfer, Malte
  • ChemNanoMat, Vol. 5, Issue 9
  • DOI: 10.1002/cnma.201900110

Electrical semiconduction modulated by light in a cobalt and naphthalene diimide metal-organic framework
journal, December 2017

  • Castaldelli, Evandro; Imalka Jayawardena, K. D. G.; Cox, David C.
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/s41467-017-02215-7

Application of a novel 2D cadmium( ii )-MOF in the formation of a photo-switch with a substantial on–off ratio
journal, January 2015

  • Roy, Sumit; Dey, Arka; Ray, Partha Pratim
  • Chemical Communications, Vol. 51, Issue 65
  • DOI: 10.1039/c5cc04323a

Water-triggered macroscopic structural transformation of a metal–organic framework
journal, January 2016

  • Ohtani, Masataka; Takase, Kazutaka; Wang, Pengyu
  • CrystEngComm, Vol. 18, Issue 11
  • DOI: 10.1039/c6ce00031b

A highly emissive and stable zinc( ii ) metal–organic framework as a host–guest chemopalette for approaching white-light-emission
journal, January 2017

  • Cai, Hong; Xu, Li-Li; Lai, He-Yun
  • Chemical Communications, Vol. 53, Issue 56
  • DOI: 10.1039/c7cc03350h

Redox-active metal–organic frameworks for energy conversion and storage
journal, January 2019

  • Calbo, Joaquín; Golomb, Matthias J.; Walsh, Aron
  • Journal of Materials Chemistry A, Vol. 7, Issue 28
  • DOI: 10.1039/c9ta04680a

Crystal structure of bis[tris(1,10-phenanthroline-κ 2 N , N ′)cobalt(II)] tetranitrate N , N ′-(1,4-phenylenedicarbonyl)diglycine solvate octahydrate
journal, July 2015

  • Pook, Niels-Patrick; Hentrich, Philipp; Gjikaj, Mimoza
  • Acta Crystallographica Section E Crystallographic Communications, Vol. 71, Issue 8
  • DOI: 10.1107/s2056989015013006