title: Incorporation of Pyrazine and Bipyridine Linkers with High-Spin Fe(II) and Co(II) in a Metal-Organic Framework.
abstract: A series of isoreticular metal-organic frameworks (MOFs) of the formula M(BDC)(L) (M = Fe(II) or Co(II), BDC = 1,4-benzenedicarboxylate, L = pyrazine (pyz) or 4,4'-bipyridine (bipy)) has been synthesized and characterized by N2gas uptake measurements, single crystal and powder X-ray diffraction, magnetometry, X-ray absorption spectroscopy, and Mössbauer spectroscopy. These studies indicate the formation of a permanently porous solid with high-spin Fe(II) and Co(II) centers that are weakly coupled, consistent with first-principles density functional theory calculations. This family of materials represents unusual examples of paramagnetic metal centers coordinated by linkers capable of mediating magnetic or electronic coupling in a porous framework. While only weak interactions are observed, the rigid 3D framework of the MOF dramatically impacts the properties of these materials when compared with close structural analogues.
authors.affiliation: Department of Chemistry, The University of Chicago , Chicago, Illinois 60637, United States.
authors.forename: Airi
authors.identifier: http://orcid.org/0000-0001-6666-6014
authors.initials: A
authors.lastname: Kawamura
authors.affiliation: Institute for Molecular Engineering, The University of Chicago , Chicago, Illinois 60637, United States.
authors.forename: Arin R
authors.identifier: http://orcid.org/0000-0002-5593-9301
authors.initials: AR
authors.lastname: Greenwood
authors.affiliation: Department of Chemistry, The University of Chicago , Chicago, Illinois 60637, United States.
authors.forename: Alexander S
authors.initials: AS
authors.lastname: Filatov
authors.affiliation: Department of Chemistry, Northwestern University , Evanston, Illinois 60208, United States.
authors.forename: Audrey T
authors.initials: AT
authors.lastname: Gallagher
authors.affiliation: Institute for Molecular Engineering, The University of Chicago , Chicago, Illinois 60637, United States.|Materials Science Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Giulia
authors.initials: G
authors.lastname: Galli
authors.affiliation: Department of Chemistry, The University of Chicago , Chicago, Illinois 60637, United States.
authors.forename: John S
authors.identifier: http://orcid.org/0000-0002-0730-3018
authors.initials: JS
authors.lastname: Anderson