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Analysis of High and Selective Uptake of CO 2 in an Oxamide‐Containing {Cu 2 (OOCR) 4 }‐Based Metal–Organic Framework
Author(s) -
Alsmail Nada H.,
Suyetin Mikhail,
Yan Yong,
Cabot Rafel,
Krap Cristina P.,
Lü Jian,
Easun Timothy L.,
Bichoutskaia Elena,
Lewis William,
Blake Alexander J.,
Schröder Martin
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201304005
Subject(s) - crystallography , oxamide , van der waals force , monoclinic crystal system , chemistry , porosity , crystal structure , molecule , materials science , organic chemistry
The porous framework [Cu 2 (H 2 O) 2 L] ⋅ 4 H 2 O ⋅ 2 DMA (H 4 L=oxalylbis(azanediyl)diisophthalic acid; DMA= N,N‐ dimethylacetamide), denoted NOTT‐125, is formed by connection of {Cu 2 (RCOO) 4 } paddlewheels with the isophthalate linkers in L 4− . A single crystal structure determination reveals that NOTT‐125 crystallises in monoclinic unit cell with a =27.9161(6), b =18.6627(4) and c =32.3643(8) Å, β =112.655(3)°, space group P 2 1 / c . The structure of this material shows fof topology, which can be viewed as the packing of two types of cages (cage A and cage B) in three‐dimensional space. Cage A is constructed from twelve {Cu 2 (OOCR) 4 } paddlewheels and six linkers to form an ellipsoid‐shaped cavity approximately 24.0 Å along its long axis and 9.6 Å across its central diameter. Cage B consists of six {Cu 2 (OOCR) 4 } units and twelve linkers and has a spherical diameter of 12.7 Å taking into account the van der Waals radii of the atoms. NOTT‐125 incorporates oxamide functionality within the pore walls, and this, combined with high porosity in desolvated NOTT‐125a, is responsible for excellent CO 2 uptake (40.1 wt % at 273 K and 1 bar) and selectivity for CO 2 over CH 4 or N 2 . Grand canonical Monte Carlo (GCMC) simulations show excellent agreement with the experimental gas isotherm data, and a computational study of the specific interactions and binding energies of both CO 2 and CH 4 with the linkers in NOTT‐125 reveals a set of strong interactions between CO 2 and the oxamide motif that are not possible with a single amide.