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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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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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Metal-Ligand Bonds02:51

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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

Coordination Compounds and Nomenclature

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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 - Tetrahedral and Square Planar Complexes02:46

Crystal Field Theory - Tetrahedral and Square Planar Complexes

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Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than...
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Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction
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Self-assembled nickel(II)-centered metal-organic square grid complexes for CO2 sensing.

M Sooraj1, R Jayakrishnan2, E Manoj1

  • 1Department of Applied Chemistry, Cochin University of Science and Technology, Kochi, Kerala 682022, India. manoje@cusat.ac.in.

Dalton Transactions (Cambridge, England : 2003)
|April 2, 2025
PubMed
Summary

New metal-organic square complexes show promise as sensitive carbon dioxide (CO2) gas sensors. These thin-film sensors, particularly complex 2, demonstrate enhanced detection capabilities, even under illumination, offering improved environmental monitoring solutions.

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Area of Science:

  • Materials Science
  • Supramolecular Chemistry
  • Environmental Science

Background:

  • Detection of hazardous carbon dioxide (CO2) gas is critical for human health, environmental safety, and achieving UN Sustainable Development Goals (SDGs).
  • Metal-organic frameworks and coordination complexes are increasingly explored for gas sensing applications due to their tunable structures and properties.

Purpose of the Study:

  • To investigate novel Ni(II) metal-organic square grid complexes as thin-film CO2 gas sensors.
  • To synthesize and characterize two new Ni(II) complexes, [Ni(HL)]4Cl4·26H2O (1) and [Ni(HL)]4(BF4)4·20H2O (2), using a thiocarbohydrazone ligand (H2L).
  • To evaluate the CO2 sensing performance of thin films fabricated from these complexes.

Main Methods:

  • Self-assembly synthesis of Ni(II) metal-organic square grid complexes.
  • Structural characterization using single crystal X-ray diffraction (SCXRD) and MALDI mass spectrometry.
  • Thermal stability analysis (thermogravimetric study) and pore volume determination (BET surface area).
  • Fabrication of thin-film sensors via drop casting and evaluation of CO2 sensing performance in chemiresistive mode, with and without white light illumination.

Main Results:

  • Two stable Ni(II) metallosupramolecular square grid complexes (1 and 2) were successfully synthesized and characterized.
  • Complex 1 exhibited a solvent accessible pore volume of 1952 Å3 (≈18.2%) and a BET surface area of 2.390 m2 g-1.
  • Complex 2 showed a higher BET surface area (4.803 m2 g-1) and semiconductor characteristics with a band gap of ~1.45 eV.
  • Both complexes demonstrated CO2 gas sensing capabilities, with complex 2 showing a response of 59% compared to 31% for complex 1.
  • CO2 sensing performance was enhanced under white light illumination, and complex 2 achieved a limit of detection of 500 ppm.

Conclusions:

  • The synthesized Ni(II) metal-organic square complexes are stable and possess semiconductor properties suitable for gas sensing.
  • Thin films of these complexes, particularly complex 2, function effectively as chemiresistive CO2 gas sensors.
  • The developed CO2 gas sensors show improved performance under illumination, with complex 2 offering superior sensitivity and a low limit of detection.