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Title: Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks

Abstract

The copper paddle-wheel is the building unit of many metal organic frameworks. Because of the ability of the copper cations to attract polar molecules, copper paddle-wheels are promising for carbon dioxide adsorption and separation. They have therefore been studied extensively, both experimentally and computationally. In this work we investigate the copper–CO 2 interaction in HKUST-1 and in two different cluster models of HKUST-1: monocopper Cu(formate) 2 and dicopper Cu 2(formate) 4. We show that density functional theory methods severely underestimate the interaction energy between copper paddle-wheels and CO 2, even including corrections for the dispersion forces. In contrast, a multireference wave function followed by perturbation theory to second order using the CASPT2 method correctly describes this interaction. The restricted open-shell Møller–Plesset 2 method (ROS-MP2, equivalent to (2,2) CASPT2) was also found to be adequate in describing the system and used to develop a novel force field. Our parametrization is able to predict the experimental CO 2 adsorption isotherms in HKUST-1, and it is shown to be transferable to other copper paddle-wheel systems.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Federal Inst. of Technology (EPFL), Lausanne (Switzerland). Inst. of Chemical Sciences and Engineering. Lab. of Molecular Simulation
  2. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry. Chemical Theory Center. Minnesota Supercomputing Inst.
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States); Federal Inst. of Technology (EPFL), Lausanne (Switzerland)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Swiss National Science Foundation (SNSF); European Research Council (ERC)
OSTI Identifier:
1369080
Grant/Contract Number:
SC0012702; 666983
Resource Type:
Journal Article: Published Article
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 28; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ongari, Daniele, Tiana, Davide, Stoneburner, Samuel J., Gagliardi, Laura, and Smit, Berend. Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b02302.
Ongari, Daniele, Tiana, Davide, Stoneburner, Samuel J., Gagliardi, Laura, & Smit, Berend. Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks. United States. doi:10.1021/acs.jpcc.7b02302.
Ongari, Daniele, Tiana, Davide, Stoneburner, Samuel J., Gagliardi, Laura, and Smit, Berend. 2017. "Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks". United States. doi:10.1021/acs.jpcc.7b02302.
@article{osti_1369080,
title = {Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks},
author = {Ongari, Daniele and Tiana, Davide and Stoneburner, Samuel J. and Gagliardi, Laura and Smit, Berend},
abstractNote = {The copper paddle-wheel is the building unit of many metal organic frameworks. Because of the ability of the copper cations to attract polar molecules, copper paddle-wheels are promising for carbon dioxide adsorption and separation. They have therefore been studied extensively, both experimentally and computationally. In this work we investigate the copper–CO2 interaction in HKUST-1 and in two different cluster models of HKUST-1: monocopper Cu(formate)2 and dicopper Cu2(formate)4. We show that density functional theory methods severely underestimate the interaction energy between copper paddle-wheels and CO2, even including corrections for the dispersion forces. In contrast, a multireference wave function followed by perturbation theory to second order using the CASPT2 method correctly describes this interaction. The restricted open-shell Møller–Plesset 2 method (ROS-MP2, equivalent to (2,2) CASPT2) was also found to be adequate in describing the system and used to develop a novel force field. Our parametrization is able to predict the experimental CO2 adsorption isotherms in HKUST-1, and it is shown to be transferable to other copper paddle-wheel systems.},
doi = {10.1021/acs.jpcc.7b02302},
journal = {Journal of Physical Chemistry. C},
number = 28,
volume = 121,
place = {United States},
year = 2017,
month = 6
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/acs.jpcc.7b02302

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  • The copper paddle-wheel is the building unit of many metal organic frameworks. Because of the ability of the copper cations to attract polar molecules, copper paddle-wheels are promising for carbon dioxide adsorption and separation. They have therefore been studied extensively, both experimentally and computationally. In this work we investigate the copper–CO 2 interaction in HKUST-1 and in two different cluster models of HKUST-1: monocopper Cu(formate) 2 and dicopper Cu 2(formate) 4. We show that density functional theory methods severely underestimate the interaction energy between copper paddle-wheels and CO 2, even including corrections for the dispersion forces. In contrast, a multireferencemore » wave function followed by perturbation theory to second order using the CASPT2 method correctly describes this interaction. The restricted open-shell Møller–Plesset 2 method (ROS-MP2, equivalent to (2,2) CASPT2) was also found to be adequate in describing the system and used to develop a novel force field. Our parametrization is able to predict the experimental CO 2 adsorption isotherms in HKUST-1, and it is shown to be transferable to other copper paddle-wheel systems.« less
  • The physical properties of [CuL{sup 1} {sub 2}(H{sub 2}O)] (1) and [CuL{sup 2} {sub 2}(H{sub 2}O)] (2) and preparation and crystal structures of the inclusion compounds 1.(P)-C{sub 2}H{sub 4}Br{sub 2}, 2.(M)-C{sub 2}H{sub 4}Br{sub 2}, 1.CH{sub 3}CN and 2.CH{sub 3}CN are described. HL{sup 1} and HL{sup 2} (H represents the dissociable phenolic proton) are the N,O-donor chiral reduced Schiff bases N-(2-hydroxy-5-nitrobenzyl)-(R)-{alpha}-methyl-benzylamine and N-(2-hydroxy-5-nitrobenzyl)-(S)-{alpha}-methylbenzylamine, respectively. All the compounds crystallize in the non-centrosymmetric space group C2. In the crystal lattice, the host [CuL {sup n} {sub 2}(H{sub 2}O)] (1 and 2) molecules connected by O-H...O and C-H...O interactions form perfectly polar two-dimensional networks.more » In these chiral and polar host frameworks, enantiospecific inclusion with polar ordering of the right-handed (P) and the left-handed (M) gauche form of 1,2-dibromoethane as well as polar alignment of acetonitrile molecules are observed. The host and guest molecules are linked by C-H...O interactions. The O-atoms of the nitro substituent on the ligands of 1 and 2 act as the acceptors in all these intermolecular O-H...O and C-H...O interactions. The structures reported in this work provide rare examples of enantiospecific trapping of the chiral rotamers of 1,2-dibromoethane as well as perfectly polar alignment of both guest and host molecules. - Graphical abstract: The square-pyramidal Cu(II) complexes [CuL {sup n} {sub 2}(H{sub 2}O)] with the bidentate HL {sup n} (HL{sup 1}=N-(2-hydroxy-5-nitrobenzyl)-(R)-{alpha}-methyl-benzylamine and HL{sup 2}=N-(2-hydroxy-5-nitrobenzyl)-(S)-{alpha}-methylbenzylamine) form 1:1 host-guest compounds with Br(CH{sub 2}){sub 2}Br and CH{sub 3}CN. The X-ray structures of these species reveal the enantiospecific confinement of the chiral rotamers of Br(CH{sub 2}){sub 2}Br and perfectly polar ordering of both host and guest molecules in the crystal lattice. The figure shows the polar alignments of (a) [CuL{sup 1} {sub 2}(H{sub 2}O)].(P)-C{sub 2}H{sub 4}Br{sub 2} and (b) [CuL{sup 2} {sub 2}(H{sub 2}O)].CH{sub 3}CN.« less
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