Single-Crystal to Single-Crystal Transformation of a Nonporous Fe(II) Metal-Organic Framework into a Porous Metal-Organic Framework via a Solid-State Reaction

Sebastian Spirkl; Maciej Grzywa; Stephan Reschke; Jonas K H Fischer; Pit Sippel; Serhiy Demeshko; Hans-Albrecht Krug von Nidda; Dirk Volkmer

doi:10.1021/acs.inorgchem.7b01818

Single-Crystal to Single-Crystal Transformation of a Nonporous Fe(II) Metal-Organic Framework into a Porous Metal-Organic Framework via a Solid-State Reaction

Inorg Chem. 2017 Oct 16;56(20):12337-12347. doi: 10.1021/acs.inorgchem.7b01818. Epub 2017 Sep 29.

Authors

Sebastian Spirkl¹, Maciej Grzywa¹, Stephan Reschke², Jonas K H Fischer², Pit Sippel², Serhiy Demeshko³, Hans-Albrecht Krug von Nidda², Dirk Volkmer¹

Affiliations

¹ University of Augsburg , Institute of Physics, Chair of Solid State and Materials Chemistry, Universitätsstrasse 1, 86159 Augsburg, Germany.
² University of Augsburg , Institute of Physics, Experimental Physics V, Center for Electronic Correlations and Magnetism, Universitätsstrasse 1, 86159 Augsburg, Germany.
³ Georg-August-Universität Göttingen , Institute of Inorganic Chemistry, Tammannstraße 4, 37077 Göttingen, Germany.

PMID: 28960968
DOI: 10.1021/acs.inorgchem.7b01818

Abstract

We report the synthesis of an air-stable nonporous coordination compound based on iron(II) centers, formate anions, and a 4,4'-bipyrazole (H₂BPZ) ligand. Upon thermal treatment, a porous metal-organic framework (MOF) formed due to decomposition of the incorporated formate anions. This decomposition step and the following structural changes constituted a single-crystal to single-crystal transformation. The resulting [Fe(BPZ)] framework contained tetrahedrally coordinated iron(II) metal centers. The framework was sensitive toward oxidation by molecular oxygen even at temperatures of 183 K, as followed by oxygen sorption measurements and a color change from colorless to metallic black. The semiconductor properties of the oxidized material were studied by diffuse reflectance UV/vis/NIR spectroscopy and dielectric spectroscopy.