title: Probing Framework-Restricted Metal Axial Ligation and Spin State Patterns in a Post-Synthetically Reduced Iron-Porphyrin-Based Metal-Organic Framework.
abstract: An iron-porphyrin-based metal organic framework PCN-222(Fe) is investigated upon postsynthetic reduction with piperidine. Fe K-edge X-ray absorption and Kβ mainline emission spectroscopy measurements reveal the local coordination geometry, oxidation, and spin state changes experienced by the Fe sites upon reaction with this axially coordinating reducing agent. Analysis and fitting of these data confirm the binding pattern predicted by a space-filling model of the structurally constrained pore environments. These results are further supported by UV-vis diffuse reflectance, IR, and resonance Raman spectroscopy data.
authors.affiliation: Department of Chemistry, Rutgers University , Newark, New Jersey 07102, United States.
authors.forename: Pavel
authors.initials: P
authors.lastname: Kucheryavy
authors.affiliation: Department of Chemistry, Rutgers University , Newark, New Jersey 07102, United States.
authors.forename: Nicole
authors.initials: N
authors.lastname: Lahanas
authors.affiliation: Department of Chemistry, Rutgers University , Newark, New Jersey 07102, United States.
authors.forename: Ever
authors.initials: E
authors.lastname: Velasco
authors.affiliation: X-ray Science Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Cheng-Jun
authors.initials: CJ
authors.lastname: Sun
authors.affiliation: Department of Chemistry, Rutgers University , Newark, New Jersey 07102, United States.
authors.forename: Jenny V
authors.initials: JV
authors.lastname: Lockard
mesh_terms: D006418:Heme / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010880:Piperidines / Q000737:chemistry; D013052:Spectrometry, X-Ray Emission; D013055:Spectrophotometry, Infrared; D013056:Spectrophotometry, Ultraviolet; D013059:Spectrum Analysis, Raman
chemical_list: D009942:Organometallic Compounds; D010880:Piperidines; D006418:Heme; C032727:piperidine; D007501:Iron