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Alkali-Metal Azides Interacting with Metal–Organic Frameworks

Authors

  • Dr. Nerina Armata,

    1. Dipartimento di Chimica “Stanislao Cannizzaro” dell'Università viale delle Scienze Ed. 17, 90128 Palermo (Italy)
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  • Dr. Remedios Cortese,

    1. Dipartimento di Chimica “Stanislao Cannizzaro” dell'Università viale delle Scienze Ed. 17, 90128 Palermo (Italy)
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  • Prof. Dario Duca,

    Corresponding author
    1. Dipartimento di Chimica “Stanislao Cannizzaro” dell'Università viale delle Scienze Ed. 17, 90128 Palermo (Italy)
    • Dipartimento di Chimica “Stanislao Cannizzaro” dell'Università viale delle Scienze Ed. 17, 90128 Palermo (Italy)
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  • Prof. Roberto Triolo

    1. Dipartimento di Chimica “Stanislao Cannizzaro” dell'Università viale delle Scienze Ed. 17, 90128 Palermo (Italy)
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    • Deceased, January 21, 2012.


Abstract

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.

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