Deceased, January 21, 2012.
Alkali-Metal Azides Interacting with Metal–Organic Frameworks
Article first published online: 19 NOV 2012
Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Volume 14, Issue 1, pages 220–226, January 14, 2013
How to Cite
Armata, N., Cortese, R., Duca, D. and Triolo, R. (2013), Alkali-Metal Azides Interacting with Metal–Organic Frameworks. ChemPhysChem, 14: 220–226. doi: 10.1002/cphc.201200752
- Issue published online: 10 JAN 2013
- Article first published online: 19 NOV 2012
- Manuscript Received: 13 SEP 2012
- alkali metals;
- density functional calculations;
- metal–organic frameworks;
Interactions between alkali-metal azides and metal–organic framework (MOF) derivatives, namely, the first and third members of the isoreticular MOF (IRMOF) family, IRMOF-1 and IRMOF-3, are studied within the density functional theory (DFT) paradigm. The investigations take into account different models of the selected IRMOFs. The mutual influence between the alkali-metal azides and the π rings or Zn centers of the involved MOF derivatives are studied by considering the interactions both of the alkali-metal cations with model aromatic centers and of the alkali-metal azides with distinct sites of differently sized models of IRMOF-1 and IRMOF-3. Several exchange and correlation functionals are employed to calculate the corresponding interaction energies. Remarkably, it is found that, with increasing alkali-metal atom size, the latter decrease for cations interacting with the π-ring systems and increase for the azides interacting with the MOF fragments. The opposite behavior is explained by stabilization effects on the azide moieties and determined by the Zn atoms, which constitute the inorganic vertices of the IRMOF species. Larger cations can, in fact, coordinate more efficiently to both the aromatic center and the azide anion, and thus stabilizing bridging arrangements of the azide between one alkali-metal and two Zn atoms in an η2 coordination mode are more favored.