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Metal-Ligand Bonds02:51

Metal-Ligand Bonds

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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...
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Coordination Compounds and Nomenclature02:54

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In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
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Crystal Field Theory - Octahedral Complexes02:58

Crystal Field Theory - Octahedral Complexes

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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...
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Coordination Number and Geometry02:57

Coordination Number and Geometry

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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.
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Colors and Magnetism03:02

Colors and Magnetism

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Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
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Valence Bond Theory02:42

Valence Bond Theory

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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...
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Packing Order Control in Conductive Metal-Organic Frameworks by Tuning Ligand Oxidation State.

Yunlong Fan1,2, Bin Jiang2, Zhenghan Zhang3

  • 1Key Laboratory of Artificial Structure and Quantum Control, Ministry of Education, School of Physics and Astronomy, Shanghai Jiao Tong University, Shanghai, 200240, P.R. China.

Angewandte Chemie (International Ed. in English)
|December 8, 2025
PubMed
Summary

Tuning ligand oxidation states in conductive metal-organic frameworks (c-MOFs) with lanthanides controls framework packing and enhances electronic transport. This strategy enables precise control over structural order and charge transport in c-MOFs.

Keywords:
Charge transportConductive MOFsOxidation statePacking controlSingle‐crystal

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Area of Science:

  • Materials Science
  • Chemistry
  • Nanotechnology

Background:

  • Conductive metal-organic frameworks (c-MOFs) offer combined porosity and charge transport.
  • Electrical performance in c-MOFs is linked to packing and ligand oxidation state, areas needing further exploration.

Purpose of the Study:

  • To investigate a strategy for controlling packing and topology in c-MOFs by tuning ligand oxidation states.
  • To explore the use of lanthanides, specifically Gadolinium (Gd), in versatile coordination chemistry for c-MOF design.

Main Methods:

  • Utilized diffuse reflectance spectroscopy to analyze ligand oxidation states.
  • Employed single-crystal transport measurements to evaluate electronic transport performance.
  • Synthesized and characterized Gd-based c-MOFs with varying ligand oxidation states.

Main Results:

  • Lower mixed oxidation states (-4 and -5) of 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) with Gd3+ resulted in ordered porous packing (Gd1.5HHTP) and superior electronic transport at low temperatures.
  • Higher oxidation state (-3) of HHTP with Gd3+ led to densely packed structures with disorder (GdHHTP) and significantly reduced electrical conductivity at elevated temperatures.

Conclusions:

  • Ligand oxidation state tuning is an effective strategy for precise control of structural order and charge transport in c-MOFs.
  • This approach provides a foundation for rationally designing c-MOFs with tunable electronic properties.
  • Lanthanide coordination chemistry offers versatile pathways for manipulating c-MOF structures and functionalities.