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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. https://doi.org/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. https://doi.org/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. https://doi.org/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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    • Chaudhari, Abhijeet K.; Kim, Ha Jin; Han, Intaek
    • Advanced Materials, Vol. 29, Issue 27
    • DOI: 10.1002/adma.201701463

    Doping of metal–organic frameworks towards resistive sensing
    journal, May 2017


    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

    Understanding and Controlling the Dielectric Response of Metal-Organic Frameworks
    journal, March 2018

    • Ryder, Matthew R.; Donà, Lorenzo; Vitillo, Jenny G.
    • ChemPlusChem, Vol. 83, Issue 4
    • DOI: 10.1002/cplu.201700558

    Elektrisch leitfähige poröse Metall-organische Gerüstverbindungen
    journal, January 2016

    • Sun, Lei; Campbell, Michael G.; Dincă, Mircea
    • Angewandte Chemie, Vol. 128, Issue 11
    • DOI: 10.1002/ange.201506219

    Thin Film Thermoelectric Metal-Organic Framework with High Seebeck Coefficient and Low Thermal Conductivity
    journal, April 2015

    • Erickson, Kristopher J.; Léonard, François; Stavila, Vitalie
    • Advanced Materials, Vol. 27, Issue 22
    • DOI: 10.1002/adma.201501078

    Photonic hybrid crystals constructed from in situ host–guest nanoconfinement of a light-emitting complex in metal–organic framework pores
    journal, January 2016

    • Chaudhari, Abhijeet K.; Ryder, Matthew R.; Tan, Jin-Chong
    • Nanoscale, Vol. 8, Issue 12
    • DOI: 10.1039/c6nr01122e

    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

    Rational modifications of PCN-700 to induce electrical conductivity: a computational study
    journal, January 2020

    • Chong, Sanggyu; Kim, Jihan
    • Dalton Transactions, Vol. 49, Issue 1
    • DOI: 10.1039/c9dt03865e

    Switching in Metal–Organic Frameworks
    journal, December 2019

    • Bigdeli, Fahime; Lollar, Christina T.; Morsali, Ali
    • Angewandte Chemie International Edition, Vol. 59, Issue 12
    • DOI: 10.1002/anie.201900666

    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

    Electrochromic thin films of Zn-based MOF-74 nanocrystals facilely grown on flexible conducting substrates at room temperature
    journal, August 2019

    • Chaudhari, Abhijeet K.; Souza, Barbara E.; Tan, Jin-Chong
    • APL Materials, Vol. 7, Issue 8
    • DOI: 10.1063/1.5108948

    Reversible Optical Writing and Data Storage in an Anthracene‐Loaded Metal‐Organic Framework
    journal, December 2018