Probing Framework-Restricted Metal Axial Ligation and Spin State Patterns in a Post-Synthetically Reduced Iron-Porphyrin-Based Metal–Organic Framework
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- 作者：Pavel Kucheryavy ; Nicole Lahanas ; Ever Velasco ; Cheng-Jun Sun ; Jenny V. Lockard
- 刊名：The Journal of Physical Chemistry Letters
- 出版年：2016
- 出版时间：April 7, 2016
- 年：2016
- 卷：7
- 期：7
- 页码：1109-1115
- 全文大小：377K
- ISSN：1948-7185
文摘
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.