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Updated: Mar 24, 2026
Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
Probing Framework-Restricted Metal Axial Ligation and Spin State Patterns in a Post-Synthetically Reduced
Pavel Kucheryavy1, Nicole Lahanas1, Ever Velasco1
1Department of Chemistry, Rutgers University , Newark, New Jersey 07102, United States.
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.
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