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Related Concept Videos

Metal-Ligand Bonds02:51

Metal-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...
Coordination Number and Geometry02:57

Coordination Number and Geometry

For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.
Complexation Equilibria: The Chelate Effect01:19

Complexation Equilibria: The Chelate Effect

In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
Crystal Field Theory - Octahedral Complexes02:58

Crystal Field Theory - Octahedral Complexes

Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
Valence Bond Theory02:42

Valence 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...
Extraction: Advanced Methods00:56

Extraction: Advanced Methods

Metal ions can be separated from one another by complexation with organic ligands–the chelating agent– to form uncharged chelates. Here, the chelating agent must contain hydrophobic groups and behave as a weak acid, losing a proton to bind with the metal. Since most organic ligands used in this process are insoluble or undergo oxidation in the aqueous phase, the chelating agent is initially added to the organic phase and extracted into the aqueous phase. The metal-ligand complex is formed in...

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Synthesis and Characterization of Functionalized Metal-organic Frameworks
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Amino Functionalization-Induced Coordination Geometry Switch Enables Pore Size Exclusion and Selective CHF3 Capture

Xi-Ting Zhang1, Li-Ping Zhang1, Zhong-Lei Xing1

  • 1State Key Laboratory of Fluorine & Nitrogen Chemicals, School of Chemical Engineering and Technology, Xi'an Jiaotong University, Xi'an, Shaanxi 710049, China.

Inorganic Chemistry
|May 19, 2026
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Summary

Ligand functionalization in metal-organic frameworks (MOFs) unexpectedly altered metal coordination, collapsing a 3D structure to 2D. This impacted gas adsorption properties, highlighting coordination geometry

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Published on: July 14, 2015

Area of Science:

  • Materials Science
  • Chemistry
  • Nanotechnology

Background:

  • Coordination geometry of metal nodes is a key factor in metal-organic framework (MOF) design.
  • Functionalization of linkers can influence MOF structure and properties.
  • Understanding these structure-property relationships is crucial for designing advanced MOFs.

Purpose of the Study:

  • To investigate the effect of an amino substituent on isonicotinic acid linkers in copper-based MOFs.
  • To determine how changes in coordination geometry impact framework dimensionality and gas adsorption.
  • To explore the potential of MOFs for selective gas separation.

Main Methods:

  • Synthesis of Cu(II)-based MOFs with isonicotinic acid (Cu-ina) and 2-aminoisonicotinic acid (Cu-2ain).
  • Characterization of MOF structures and coordination geometries.
  • Gas adsorption measurements (CHF3, N2) and selectivity calculations (IAST).
  • Computational studies including GCMC simulations and DFT calculations to confirm bonding interactions.

Main Results:

  • The amino substituent in 2-aminoisonicotinic acid induced a switch in Cu(II) coordination from five-coordinate square-pyramidal to four-coordinate square-planar.
  • This structural change collapsed the 3D microporous Cu-ina framework into a 2D layered structure (Cu-2ain).
  • Cu-2ain exhibited a reduced pore-limiting diameter (3.27 Å), leading to complete size exclusion of CHF3 and N2.
  • The 3D Cu-ina framework showed a high CHF3 uptake (50.1 cm3 g-1) and a CHF3/N2 selectivity of 46, driven by specific hydrogen bonding.
  • Computational studies confirmed the role of cooperative C-H···F and C-H···O hydrogen bonding in Cu-ina's selectivity.

Conclusions:

  • Ligand functionalization can inadvertently alter metal coordination geometry and framework dimensionality.
  • Structural collapse can override intended surface-chemical benefits of functionalization.
  • Careful consideration of coordination geometry is essential for rational MOF design.
  • The studied MOFs demonstrate potential for selective gas separation applications.