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Imparting gas selective and pressure dependent porosity into a non-porous solid: Via coordination flexibility

Accepted version
Peer-reviewed

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Authors

Nandi, S 
De Luna, P 
Maity, R 
Chakraborty, D 

Abstract

Using a simple hard-soft acid-base concept we have deliberately designed gas-specific and pressure dependent porosity into a non-porous solid via coordination flexibility. This creates distinct gate-openings wherein the CO2 molecule opens-up the framework pores by rotating the ligand about the weaker hard-soft bonds (hard-soft gate control). For this, we have studied the CO2 gating behaviour of M(4-PyC)2 (M = Mg, Mn and Cu), which represent metals of varying hardness. A combination of quantum chemical calculations, molecular dynamics and Grand canonical Monte Carlo simulations were performed to examine the gate opening of the isonicotinate ligands in Mg(4-PyC)2. The simulations show that interaction of the CO2 molecules with the isonicotinate ligands at different CO2 loadings can result in pressure-dependent gate opening. Furthermore, the simulated CO2 uptake values calculated using the partially gate-opened structures at different loadings showed good agreement with the experimental uptake values. This provides an effective strategy for designing highly-stable dynamic porous solids employing rigid frameworks.

Description

Keywords

34 Chemical Sciences, 3407 Theoretical and Computational Chemistry

Journal Title

Materials Horizons

Conference Name

Journal ISSN

2051-6347
2051-6355

Volume Title

6

Publisher

Royal Society of Chemistry (RSC)

Rights

All rights reserved