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Title: Backbonding contributions to small molecule chemisorption in a metal–organic framework with open copper( i ) centers

Abstract

Metal–organic frameworks are promising materials for applications such as gas capture, separation, and storage, due to their ability to selectively adsorb small molecules. The metal–organic framework CuI-MFU-4I, which contains coordinatively unsaturated copper(I) centers, can engage in backbonding interactions with various small molecule guests, motivating the design of frameworks that engage in backbonding and other electronic interactions for highly efficient and selective adsorption. Here, we examine several gases expected to bind to the open copper(I) sites in CuI-MFU-4I via different electronic interactions, including σ-donation, π-backbonding, and formal electron transfer. We show that in situ Cu L-edge near edge X-ray absorption fine structure (NEXAFS) spectroscopy can elucidate π-backbonding by directly probing excitations to unoccupied backbonding orbitals with Cu d-character, even for gases that participate in other dominant interactions, such as ligand-to-metal σ-donation. First-principles calculations based on density functional theory and time-dependent density functional theory additionally reveal the backbonding molecular orbitals associated with these spectroscopic transitions. The energies of the transitions correlate with the energy levels of the isolated small molecule adsorbates, and the transition intensities are proportional to the binding energies of the guest molecules within CuI-MFU-4I. By elucidating the molecular and electronic structure origins of backbonding interactions between electron rich metalmore » centers in metal–organic frameworks and small molecule guests, it is possible to develop guidelines for further molecular-level design of solid-state adsorbents for energy-efficient separations of relevance to industry.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [3];  [2]; ORCiD logo [1]
  1. Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, USA
  2. The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, USA
  3. Department of Chemistry, University of California, Berkeley, Berkeley, USA, Materials Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1755461
Alternate Identifier(s):
OSTI ID: 1766537
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 12 Journal Issue: 6; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Su, Gregory M., Wang, Han, Barnett, Brandon R., Long, Jeffrey R., Prendergast, David, and Drisdell, Walter S.. Backbonding contributions to small molecule chemisorption in a metal–organic framework with open copper( i ) centers. United Kingdom: N. p., 2021. Web. https://doi.org/10.1039/D0SC06038K.
Su, Gregory M., Wang, Han, Barnett, Brandon R., Long, Jeffrey R., Prendergast, David, & Drisdell, Walter S.. Backbonding contributions to small molecule chemisorption in a metal–organic framework with open copper( i ) centers. United Kingdom. https://doi.org/10.1039/D0SC06038K
Su, Gregory M., Wang, Han, Barnett, Brandon R., Long, Jeffrey R., Prendergast, David, and Drisdell, Walter S.. Thu . "Backbonding contributions to small molecule chemisorption in a metal–organic framework with open copper( i ) centers". United Kingdom. https://doi.org/10.1039/D0SC06038K.
@article{osti_1755461,
title = {Backbonding contributions to small molecule chemisorption in a metal–organic framework with open copper( i ) centers},
author = {Su, Gregory M. and Wang, Han and Barnett, Brandon R. and Long, Jeffrey R. and Prendergast, David and Drisdell, Walter S.},
abstractNote = {Metal–organic frameworks are promising materials for applications such as gas capture, separation, and storage, due to their ability to selectively adsorb small molecules. The metal–organic framework CuI-MFU-4I, which contains coordinatively unsaturated copper(I) centers, can engage in backbonding interactions with various small molecule guests, motivating the design of frameworks that engage in backbonding and other electronic interactions for highly efficient and selective adsorption. Here, we examine several gases expected to bind to the open copper(I) sites in CuI-MFU-4I via different electronic interactions, including σ-donation, π-backbonding, and formal electron transfer. We show that in situ Cu L-edge near edge X-ray absorption fine structure (NEXAFS) spectroscopy can elucidate π-backbonding by directly probing excitations to unoccupied backbonding orbitals with Cu d-character, even for gases that participate in other dominant interactions, such as ligand-to-metal σ-donation. First-principles calculations based on density functional theory and time-dependent density functional theory additionally reveal the backbonding molecular orbitals associated with these spectroscopic transitions. The energies of the transitions correlate with the energy levels of the isolated small molecule adsorbates, and the transition intensities are proportional to the binding energies of the guest molecules within CuI-MFU-4I. By elucidating the molecular and electronic structure origins of backbonding interactions between electron rich metal centers in metal–organic frameworks and small molecule guests, it is possible to develop guidelines for further molecular-level design of solid-state adsorbents for energy-efficient separations of relevance to industry.},
doi = {10.1039/D0SC06038K},
journal = {Chemical Science},
number = 6,
volume = 12,
place = {United Kingdom},
year = {2021},
month = {2}
}

Journal Article:
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https://doi.org/10.1039/D0SC06038K

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