Assessment of Adsorbate π‑Backbonding in Copper(I) Metal–Organic Frameworks via Multinuclear NMR Spectroscopy and Density Functional Theory Calculations
Abstract
We assess the binding of C2H4 to the coordinately unsaturated copper(I) sites of the metal-organic frameworks Cu(I)-ZrTpmC* and Cu(I)-MFU-4l via 13C solid-state nuclear magnetic resonance spectroscopy, density functional theory (DFT), and natural localized molecular orbital analysis. Using these methods, forward-donation and back-donation contributions between C2H4 and the exposed Cu(I) are delineated, and high binding enthalpies are contextualized as a function of electronic changes upon site modification and adsorption. With the infrastructure for DFT and solid-state 13C NMR becoming more routine for scientists, we envision that these results will support the study of exposed electron-rich metal sites in a variety of chemical applications.
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