Related Experiment Video
Updated: May 16, 2026
07:14
Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
Alkali-metal azides interacting with metal-organic frameworks
Nerina Armata1, Remedios Cortese, Dario Duca
1Dipartimento di Chimica Stanislao Cannizzaro dell'Università viale delle Scienze Ed. 17, 90128 Palermo, Italy.
Summary
Density functional theory investigated alkali-metal azides and metal-organic framework (MOF) interactions. Larger alkali-metal cations enhanced azide binding to MOF fragments, favoring specific coordination modes.
Area of Science:
- Computational Chemistry
- Materials Science
- Nanotechnology
Background:
- Metal-organic frameworks (MOFs) offer tunable structures for diverse applications.
- Alkali-metal azides are potential functional components in advanced materials.
- Understanding host-guest interactions within MOFs is crucial for material design.
Purpose of the Study:
- To investigate the interactions between alkali-metal azides and IRMOF-1/IRMOF-3 using DFT.
- To elucidate the influence of alkali-metal cation size on binding affinities.
- To explore coordination modes between azides and MOF components (π-rings, Zn centers).
Main Methods:
- Density Functional Theory (DFT) calculations were employed.
- Various exchange and correlation functionals were utilized.
- Interaction energies were computed for different MOF models and alkali-metal azides.
Main Results:
- Interaction energies decreased for cations with π-ring systems as alkali-metal size increased.
- Interaction energies increased for azides with MOF fragments as alkali-metal size increased.
- Larger cations promoted bridging arrangements of azide between alkali-metal and Zn atoms (η(2) coordination).
Conclusions:
- Alkali-metal size significantly impacts binding interactions within MOFs.
- Zn atoms play a key role in stabilizing azide moieties via coordination.
- DFT provides valuable insights into designing MOF-based materials with alkali-metal azides.
Related Concept Videos
02:51Metal-Ligand Bonds
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
01:23Properties of Organometallic Compounds
Organometallic compounds are compounds that contain a carbon–metal bond. Carbon belongs to an organyl group like alkyl, aryl, allyl, or benzyl groups. The metal can be from Group I or Group II of the periodic table, a transition metal, or a semimetal.
01:09Complexation Equilibria: Factors Influencing Stability of Complexes
In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
03:45Formation of Complex Ions
A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
01:20Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...
02:42Valence Bond Theory
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...