title: 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.affiliation: Department of Chemistry, University of California, Berkeley, and Lawrence Berkeley National Laboratory, Berkeley, CA 94720; Department of Chemistry, Northwestern University, Evanston, IL 60201;
authors.forename: Andrew C-H
authors.initials: AC
authors.lastname: Sue
authors.affiliation: Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA 94720; and.
authors.forename: Ranjan V
authors.initials: RV
authors.lastname: Mannige
authors.affiliation: Department of Chemistry, University of California, Berkeley, and Lawrence Berkeley National Laboratory, Berkeley, CA 94720;
authors.forename: Hexiang
authors.initials: H
authors.lastname: Deng
authors.affiliation: Department of Chemistry, Northwestern University, Evanston, IL 60201;
authors.forename: Dennis
authors.initials: D
authors.lastname: Cao
authors.affiliation: Department of Chemistry, Northwestern University, Evanston, IL 60201;
authors.forename: Cheng
authors.initials: C
authors.lastname: Wang
authors.affiliation: Department of Chemistry, University of California, Berkeley, and Lawrence Berkeley National Laboratory, Berkeley, CA 94720;
authors.forename: Felipe
authors.initials: F
authors.lastname: Gándara
authors.affiliation: Department of Chemistry, Northwestern University, Evanston, IL 60201; yaghi@berkeley.edu stoddart@northwestern.edu SWhitelam@lbl.gov.
authors.forename: J Fraser
authors.initials: JF
authors.lastname: Stoddart
authors.affiliation: Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA 94720; and yaghi@berkeley.edu stoddart@northwestern.edu SWhitelam@lbl.gov.
authors.forename: Stephen
authors.initials: S
authors.lastname: Whitelam
authors.affiliation: Department of Chemistry, University of California, Berkeley, and Lawrence Berkeley National Laboratory, Berkeley, CA 94720; Kavli Energy NanoScience Institute, Berkeley, CA 94720 yaghi@berkeley.edu stoddart@northwestern.edu SWhitelam@lbl.gov.
authors.forename: Omar M
authors.initials: OM
authors.lastname: Yaghi
mesh_terms: D000465:Algorithms; D003198:Computer Simulation; D018360:Crystallography, X-Ray; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D008670:Metals / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D009010:Monte Carlo Method; D009942:Organometallic Compounds / Q000737:chemistry*; D012996:Solutions; D013816:Thermodynamics
chemical_list: D008670:Metals; D009942:Organometallic Compounds; D012996:Solutions
keywords: Monte Carlo simulation; metal–organic framework; out of equilibrium; polycrystalline