skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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:
Journal Article: 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. 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. 2015. "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},
url = {https://www.osti.gov/biblio/1235927}, journal = {Journal of Physical Chemistry Letters},
issn = {1948-7185},
number = 7,
volume = 6,
place = {United States},
year = {Thu Mar 19 00:00:00 EDT 2015},
month = {Thu Mar 19 00:00:00 EDT 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 131 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

A Chemically Functionalizable Nanoporous Material [Cu3(TMA)2(H2O)3]n
journal, February 1999


Design and synthesis of an exceptionally stable and highly porous metal-organic framework
journal, November 1999


Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage
journal, January 2002


A Roadmap to Implementing Metal-Organic Frameworks in Electronic Devices: Challenges and Critical Directions
journal, September 2011


MOF-based electronic and opto-electronic devices
journal, January 2014


Tuning the Ferroelectric Polarization in a Multiferroic Metal–Organic Framework
journal, November 2013


A Highly Thermally Stable Ferroelectric Metal–Organic Framework and Its Thin Film with Substrate Surface Nature Dependent Morphology
journal, August 2011


When metal organic frameworks turn into linear magnets
journal, March 2013


Two 3D metal–organic frameworks with different topologies, thermal stabilities and magnetic properties
journal, January 2012


First-Principles Study of Microporous Magnets M-MOF-74 (M = Ni, Co, Fe, Mn): the Role of Metal Centers
journal, August 2013


A Water-Stable Metal–Organic Framework with Highly Acidic Pores for Proton-Conducting Applications
journal, January 2013


Proton Conduction in Metal-Organic Frameworks and Related Modularly Built Porous Solids
journal, January 2013


Ion Conductivity and Transport by Porous Coordination Polymers and Metal–Organic Frameworks
journal, June 2013


Metal organic frameworks for electrochemical applications
journal, January 2012


Luminescent metal–organic frameworks
journal, January 2009


Engineering metal-based luminescence in coordination polymers and metal–organic frameworks
journal, January 2013


Porous, Conductive Metal-Triazolates and Their Structural Elucidation by the Charge-Flipping Method
journal, June 2012


Conductivity, Doping, and Redox Chemistry of a Microporous Dithiolene-Based Metal−Organic Framework
journal, July 2010


High Charge Mobility in a Tetrathiafulvalene-Based Microporous Metal–Organic Framework
journal, July 2012


Large-scale screening of hypothetical metal–organic frameworks
journal, November 2011


Tunable Electrical Conductivity in Metal-Organic Framework Thin-Film Devices
journal, December 2013


Charge-transfer guest interactions in luminescent MOFs: implications for solid-state temperature and environmental sensing
journal, January 2012


Metal–Organic Framework Materials as Chemical Sensors
journal, September 2011


Molecular decoding using luminescence from an entangled porous framework
journal, January 2011


Design and synthesis of metal–organic frameworks using metal–organic polyhedra as supermolecular building blocks
journal, January 2009


From Molecules to Crystal Engineering:  Supramolecular Isomerism and Polymorphism in Network Solids
journal, June 2001


Connecting structure with function in metal–organic frameworks to design novel photo- and radioluminescent materials
journal, January 2012


Ab-initio prediction of materials properties with CRYSTAL: MOF-5 as a case study
journal, January 2006


Electronic structure and properties of isoreticular metal-organic frameworks: The case of M-IRMOF1 (M=Zn, Cd, Be, Mg, and Ca)
journal, September 2005


Influence of Connectivity and Porosity on Ligand-Based Luminescence in Zinc Metal−Organic Frameworks
journal, June 2007


Do Special Noncovalent π–π Stacking Interactions Really Exist?
journal, April 2008


Rethinking the term “pi-stacking”
journal, January 2012


Semiconductor Behavior of a Metal-Organic Framework (MOF)
journal, June 2007


Metal–organic frameworks as semiconductors
journal, January 2010


Electronic and vibrational properties of a MOF-5 metal–organic framework: ZnO quantum dot behaviour
journal, January 2004


High Capacity Hydrogen Adsorption in Cu(II) Tetracarboxylate Framework Materials: The Role of Pore Size, Ligand Functionalization, and Exposed Metal Sites
journal, February 2009


CW and Pulsed ESR Spectroscopy of Cupric Ions in the Metal−Organic Framework Compound Cu 3 (BTC) 2
journal, February 2008


Cooperative magnetic behavior in the coordination polymers [Cu3(TMA)2L3] (L=H2O, pyridine)
journal, May 2000


Interdimer exchange in linear chain copper acetate-pyrazine
journal, January 1974


The electronic spectrum of binuclear copper acetate monohydrate
journal, January 1972


Detailed spectral studies of copper acetate: excited-state interactions in copper dimers
journal, May 1989


Electronic structure of copper acetate monohydrate based on a coupled chromophore model
journal, January 1965


Charge Photogeneration in Organic Solar Cells
journal, November 2010


Exciton diffusion in organic photovoltaic cells
journal, January 2014


The Evolution of Organometallic Complexes in Organic Light-Emitting Devices
journal, September 2007


Energy transfer in supramolecular materials for new applications in photonics and electronics
journal, July 2014


Spectral- and Pulse-Shape Discrimination in Triplet-Harvesting Plastic Scintillators
journal, December 2012


Importance of the Donor:Fullerene Intermolecular Arrangement for High-Efficiency Organic Photovoltaics
journal, June 2014


A route to high surface area, porosity and inclusion of large molecules in crystals
journal, February 2004


A Shift from Diffusion Assisted to Energy Transfer Controlled Fluorescence Quenching in Polymer–Fullerene Photovoltaic Blends
journal, November 2012


Large-Pore Apertures in a Series of Metal-Organic Frameworks
journal, May 2012


High Electrical Conductivity in Ni 3 (2,3,6,7,10,11-hexaiminotriphenylene) 2 , a Semiconducting Metal–Organic Graphene Analogue
journal, April 2014


Electrical switching and memory phenomena in Cu‐TCNQ thin films
journal, March 1979


Electron transfer in a new highly conducting donor-acceptor complex
journal, February 1973


Control of Charge Transfer in a Series of Ru 2 II,II /TCNQ Two-Dimensional Networks by Tuning the Electron Affinity of TCNQ Units: A Route to Synergistic Magnetic/Conducting Materials
journal, February 2010


Electron transfer at the class II/III borderline of mixed valency: dependence of rates on solvent dynamics and observation of a localized-to-delocalized transition in freezing solvents
journal, September 2007

  • Glover, Starla D.; Lear, Benjamin J.; Salsman, J. Catherine
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 366, Issue 1862
  • https://doi.org/10.1098/rsta.2007.2149

Solvent Dynamical Control of Ultrafast Ground State Electron Transfer:  Implications for Class II−III Mixed Valency
journal, October 2007


Electronic conductivity in Berlin green and Prussian blue
journal, April 2011


Raman spectra of conducting TCNQ salts; Estimation of the degree of charge transfer from vibrational frequencies
journal, January 1980


Hexagonal Layered Materials Composed of [M2(O2CCF3)4] (M=Ru and Rh) Donors and TCNQ Acceptors
journal, November 2000


Charge Transfer on the Nanoscale:  Current Status
journal, July 2003


Probing Hopping Conduction in Conjugated Molecular Wires Connected to Metal Electrodes
journal, February 2011


Works referencing / citing this record:

Reversible Optical Writing and Data Storage in an Anthracene‐Loaded Metal–Organic Framework
journal, February 2019


Defective Metal-Organic Frameworks
journal, January 2018


Electroactive Metalorganic Frameworks
journal, October 2018


New OLEDs Based on Zirconium Metal-Organic Framework
journal, January 2018


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


Achieving current rectification ratios ≥ 10 5 across thin films of coordination polymer
journal, January 2019


Electrically Conductive Porous Metal-Organic Frameworks
journal, January 2016


Exploiting redox activity in metal–organic frameworks: concepts, trends and perspectives
journal, January 2016


Rational approach to guest confinement inside MOF cavities for low-temperature catalysis
journal, March 2019


A porous, electrically conductive hexa-zirconium( iv ) metal–organic framework
journal, January 2018


Strategies to Improve Electrical and Ionic Conductivities of Metal–Organic Frameworks
journal, December 2019


An updated roadmap for the integration of metal–organic frameworks with electronic devices and chemical sensors
journal, January 2017


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


High electrical conductivity and high porosity in a Guest@MOF material: evidence of TCNQ ordering within Cu 3 BTC 2 micropores
journal, January 2018


Schalten in Metall‐organischen Gerüsten
journal, December 2019


Optochemically Responsive 2D Nanosheets of a 3D Metal-Organic Framework Material
journal, May 2017


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


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


Elektrisch leitfähige poröse Metall-organische Gerüstverbindungen
journal, January 2016


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


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


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


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


Switching in Metal–Organic Frameworks
journal, December 2019


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


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


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


Doping of metal-organic frameworks towards resistive sensing
preprint, January 2016


Metal–Organic Framework Co-MOF-74-Based Host–Guest Composites for Resistive Gas Sensing
text, January 2019


Doping of metal-organic frameworks towards resistive sensing
preprint, January 2016