Heterogeneity of functional groups in a metal-organic framework displays magic number ratios
Abstract
Multiple organic functionalities can now be apportioned into nanoscale domains within a metal-coordinated framework, posing the following question: how do we control the resulting combination of “heterogeneity and order”? Here, we report the creation of a metal–organic framework, MOF-2000, whose two component types are incorporated in a 2:1 ratio, even when the ratio of component types in the starting solution is varied by an order of magnitude. Statistical mechanical modeling suggests that this robust 2:1 ratio has a nonequilibrium origin, resulting from kinetic trapping of component types during framework growth. Our simulations show how other “magic number” ratios of components can be obtained by modulating the topology of a framework and the noncovalent interactions between component types, a finding that may aid the rational design of functional multicomponent materials.
- Authors:
-
- LBNL
- (
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- DOE - BASIC ENERGY SCIENCESFOREIGNOTHER
- OSTI Identifier:
- 1182321
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Proc. Natl. Acad. Sci. USA
- Additional Journal Information:
- Journal Volume: 112; Journal Issue: (18) ; 05, 2015
- Country of Publication:
- United States
- Language:
- ENGLISH
Citation Formats
Sue, Andrew C.-H., Mannige, Ranjan V., Deng, Hexiang, Cao, Dennis, Wang, Cheng, Gándara, Felipe, Stoddart, J. Fraser, Whitelam, Stephen, Yaghi, Omar M., NWU), and UCB). Heterogeneity of functional groups in a metal-organic framework displays magic number ratios. United States: N. p., 2015.
Web. doi:10.1073/pnas.1416417112.
Sue, Andrew C.-H., Mannige, Ranjan V., Deng, Hexiang, Cao, Dennis, Wang, Cheng, Gándara, Felipe, Stoddart, J. Fraser, Whitelam, Stephen, Yaghi, Omar M., NWU), & UCB). Heterogeneity of functional groups in a metal-organic framework displays magic number ratios. United States. https://doi.org/10.1073/pnas.1416417112
Sue, Andrew C.-H., Mannige, Ranjan V., Deng, Hexiang, Cao, Dennis, Wang, Cheng, Gándara, Felipe, Stoddart, J. Fraser, Whitelam, Stephen, Yaghi, Omar M., NWU), and UCB). Wed .
"Heterogeneity of functional groups in a metal-organic framework displays magic number ratios". United States. https://doi.org/10.1073/pnas.1416417112. https://www.osti.gov/servlets/purl/1182321.
@article{osti_1182321,
title = {Heterogeneity of functional groups in a metal-organic framework displays magic number ratios},
author = {Sue, Andrew C.-H. and Mannige, Ranjan V. and Deng, Hexiang and Cao, Dennis and Wang, Cheng and Gándara, Felipe and Stoddart, J. Fraser and Whitelam, Stephen and Yaghi, Omar M. and NWU) and UCB)},
abstractNote = {Multiple organic functionalities can now be apportioned into nanoscale domains within a metal-coordinated framework, posing the following question: how do we control the resulting combination of “heterogeneity and order”? Here, we report the creation of a metal–organic framework, MOF-2000, whose two component types are incorporated in a 2:1 ratio, even when the ratio of component types in the starting solution is varied by an order of magnitude. Statistical mechanical modeling suggests that this robust 2:1 ratio has a nonequilibrium origin, resulting from kinetic trapping of component types during framework growth. Our simulations show how other “magic number” ratios of components can be obtained by modulating the topology of a framework and the noncovalent interactions between component types, a finding that may aid the rational design of functional multicomponent materials.},
doi = {10.1073/pnas.1416417112},
journal = {Proc. Natl. Acad. Sci. USA},
number = (18) ; 05, 2015,
volume = 112,
place = {United States},
year = {Wed May 20 00:00:00 EDT 2015},
month = {Wed May 20 00:00:00 EDT 2015}
}
Web of Science
Works referenced in this record:
Multiple Functional Groups of Varying Ratios in Metal-Organic Frameworks
journal, February 2010
- Deng, H.; Doonan, C. J.; Furukawa, H.
- Science, Vol. 327, Issue 5967, p. 846-850
Mapping of Functional Groups in Metal-Organic Frameworks
journal, July 2013
- Kong, X.; Deng, H.; Yan, F.
- Science, Vol. 341, Issue 6148, p. 882-885
Design and synthesis of an exceptionally stable and highly porous metal-organic framework
journal, November 1999
- Li, Hailian; Eddaoudi, Mohamed; M., O'Keeffe
- Nature, Vol. 402, Issue 6759, p. 276-279
Functional Porous Coordination Polymers
journal, April 2004
- Kitagawa, Susumu; Kitaura, Ryo; Noro, Shin-ichiro
- Angewandte Chemie International Edition, Vol. 43, Issue 18, p. 2334-2375
A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area
journal, September 2005
- Ferey, G.; Mellot-Draznieks, C.; Serre, C.
- Science, Vol. 309, Issue 5743, p. 2040-2042
The Reticular Chemistry Structure Resource (RCSR) Database of, and Symbols for, Crystal Nets
journal, December 2008
- O’Keeffe, Michael; Peskov, Maxim A.; Ramsden, Stuart J.
- Accounts of Chemical Research, Vol. 41, Issue 12, p. 1782-1789
Deconstructing the Crystal Structures of Metal–Organic Frameworks and Related Materials into Their Underlying Nets
journal, September 2011
- O’Keeffe, Michael; Yaghi, Omar M.
- Chemical Reviews, Vol. 112, Issue 2, p. 675-702
Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage
journal, January 2002
- Eddaoudi, Mohamed; Kim, Jaheon; Rosi, Nathaniel
- Science, Vol. 295, Issue 5554, p. 469-472
A series of isoreticular chiral metal–organic frameworks as a tunable platform for asymmetric catalysis
journal, July 2010
- Ma, Liqing; Falkowski, Joseph M.; Abney, Carter
- Nature Chemistry, Vol. 2, Issue 10
Large-Pore Apertures in a Series of Metal-Organic Frameworks
journal, May 2012
- Deng, H.; Grunder, S.; Cordova, K. E.
- Science, Vol. 336, Issue 6084, p. 1018-1023
Docking in Metal-Organic Frameworks
journal, August 2009
- Li, Qiaowei; Zhang, Wenyu; Miljanic, Ognjen S.
- Science, Vol. 325, Issue 5942, p. 855-859
A Two-Dimensional Polyrotaxane with Large Cavities and Channels: A Novel Approach to Metal-Organic Open-Frameworks by Using Supramolecular Building Blocks
journal, January 2001
- Lee, Eunsung; Kim, Jaheon; Heo, Jungseok
- Angewandte Chemie International Edition, Vol. 40, Issue 2
A Catenated Strut in a Catenated Metal-Organic Framework
journal, August 2010
- Li, Qiaowei; Sue, Chi-Hau; Basu, Subhadeep
- Angewandte Chemie International Edition, Vol. 49, Issue 38, p. 6751-6755
Anion-directed assembly of a three-dimensional metal–organic rotaxane framework
journal, January 2011
- Gong, Han-Yuan; Rambo, Brett M.; Cho, Won
- Chemical Communications, Vol. 47, Issue 21
Metal-Organic Frameworks Incorporating Copper-Complexed Rotaxanes
journal, January 2012
- Coskun, Ali; Hmadeh, Mohamad; Barin, Gokhan
- Angewandte Chemie International Edition, Vol. 51, Issue 9, p. 2160-2163
Metal–organic frameworks with dynamic interlocked components
journal, May 2012
- Vukotic, V. Nicholas; Harris, Kristopher J.; Zhu, Kelong
- Nature Chemistry, Vol. 4, Issue 6
Functional Metal–Organic Frameworks via Ligand Doping: Influences of Ligand Charge and Steric Demand
journal, January 2014
- Wang, Cheng; Liu, Demin; Xie, Zhigang
- Inorganic Chemistry, Vol. 53, Issue 3
Amphidynamic Character of Crystalline MOF-5: Rotational Dynamics of Terephthalate Phenylenes in a Free-Volume, Sterically Unhindered Environment
journal, March 2008
- Gould, Stephanie L.; Tranchemontagne, David; Yaghi, Omar M.
- Journal of the American Chemical Society, Vol. 130, Issue 11, p. 3246-3247
Internal Functionalization of Three-Dimensional Covalent Organic Frameworks
journal, January 2012
- Bunck, David N.; Dichtel, William R.
- Angewandte Chemie International Edition, Vol. 51, Issue 8
Kinetically driven ordered phase formation in binary colloidal crystals
journal, February 2013
- Bochicchio, D.; Videcoq, A.; Ferrando, R.
- Physical Review E, Vol. 87, Issue 2
Dynamical lattice gases and inherent structure in condensed phases
journal, January 1988
- Stillinger, F. H.
- The Journal of Chemical Physics, Vol. 88, Issue 1
Real-space analysis of inherent structures
journal, August 2005
- Bertin, E.
- Europhysics Letters (EPL), Vol. 71, Issue 3
Three-Dimensional Architectures Incorporating Stereoregular Donor-Acceptor Stacks
journal, May 2013
- Cao, Dennis; Juríček, Michal; Brown, Zachary J.
- Chemistry - A European Journal, Vol. 19, Issue 26
Evidence for Out-of-Equilibrium Crystal Nucleation in Suspensions of Oppositely Charged Colloids
journal, August 2007
- Sanz, Eduardo; Valeriani, Chantal; Frenkel, Daan
- Physical Review Letters, Vol. 99, Issue 5
Competing nucleation pathways in a mixture of oppositely charged colloids: Out-of-equilibrium nucleation revisited
journal, December 2009
- Peters, Baron
- The Journal of Chemical Physics, Vol. 131, Issue 24
Probing interfacial equilibration in microsphere crystals formed by DNA-directed assembly
journal, November 2008
- Kim, Anthony J.; Scarlett, Raynaldo; Biancaniello, Paul L.
- Nature Materials, Vol. 8, Issue 1
Computational analysis of binary segregation during colloidal crystallization with DNA-mediated interactions
journal, June 2010
- Scarlett, Raynaldo T.; Crocker, John C.; Sinno, Talid
- The Journal of Chemical Physics, Vol. 132, Issue 23
A mechanistic view of binary colloidal superlattice formation using DNA-directed interactions
journal, January 2011
- Scarlett, Raynaldo T.; Ung, Marie T.; Crocker, John C.
- Soft Matter, Vol. 7, Issue 5
Self-Assembly of Multicomponent Structures In and Out of Equilibrium
journal, December 2012
- Whitelam, Stephen; Schulman, Rebecca; Hedges, Lester
- Physical Review Letters, Vol. 109, Issue 26
A Two-Dimensional Polyrotaxane with Large Cavities and Channels: A Novel Approach to Metal-Organic Open-Frameworks by Using Supramolecular Building Blocks
journal, January 2001
- Lee, Eunsung; Kim, Jaheon; Heo, Jungseok
- Angewandte Chemie, Vol. 113, Issue 2
Metal-Organic Frameworks Incorporating Copper-Complexed Rotaxanes
journal, January 2012
- Coskun, Ali; Hmadeh, Mohamad; Barin, Gokhan
- Angewandte Chemie, Vol. 124, Issue 9
Functional Porous Coordination Polymers
journal, July 2004
- Kitagawa, Susumu; Kitaura, Ryo; Noro, Shin-ichiro
- ChemInform, Vol. 35, Issue 29
Internal Functionalization of Three-Dimensional Covalent Organic Frameworks
journal, January 2012
- Bunck, David N.; Dichtel, William R.
- Angewandte Chemie, Vol. 124, Issue 8
A Catenated Strut in a Catenated Metal-Organic Framework
journal, August 2010
- Li, Qiaowei; Sue, Chi-Hau; Basu, Subhadeep
- Angewandte Chemie, Vol. 122, Issue 38
Evidence for out-of-equilibrium crystal nucleation in suspensions of oppositely charged colloids
text, January 2007
- Sanz, Eduardo; Valeriani, Chantal; Frenkel, Daan
- arXiv
Self-assembly of multicomponent structures in and out of equilibrium
text, January 2012
- Whitelam, Stephen; Schulman, Rebecca; Hedges, Lester
- arXiv
Works referencing / citing this record:
The Chemistry of Reticular Framework Nanoparticles: MOF, ZIF, and COF Materials
journal, February 2020
- Ploetz, Evelyn; Engelke, Hanna; Lächelt, Ulrich
- Advanced Functional Materials, Vol. 30, Issue 41
Synthetic Strategies and Structural Arrangements of Isoreticular Mixed‐Component Metal–Organic Frameworks
journal, January 2019
- Bitzer, Johannes; Kleist, Wolfgang
- Chemistry – A European Journal, Vol. 25, Issue 8
Retrosynthesis of multi-component metal−organic frameworks
journal, February 2018
- Yuan, Shuai; Qin, Jun-Sheng; Li, Jialuo
- Nature Communications, Vol. 9, Issue 1
Site-specific metal and ligand substitutions in a microporous Mn 2+ -based metal–organic framework
journal, January 2016
- Huxley, Michael; Coghlan, Campbell J.; Burgun, Alexandre
- Dalton Transactions, Vol. 45, Issue 10
Design principles for nonequilibrium self-assembly
journal, November 2016
- Nguyen, Michael; Vaikuntanathan, Suriyanarayanan
- Proceedings of the National Academy of Sciences, Vol. 113, Issue 50
Retrosynthesis of multi-component metal−organic frameworks
journal, February 2018
- Yuan, Shuai; Qin, Jun-Sheng; Li, Jialuo
- Nature Communications, Vol. 9, Issue 1