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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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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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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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Paramagnets are materials with unpaired electrons that possess a finite magnetic moment. In the absence of a magnetic field, these moments are randomly oriented, and thus the net moment is zero. Under an external field, a torque acting on the moments tends to align them along the field's direction. However, the random thermal motion of electrons produces a torque opposite to the external field and tries to disorient the moments. These two competing effects align only a few moments along the...
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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.
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The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the...
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Proton-Conducting Magnetic Coordination Polymers.

Soumava Biswas1, Himanshu Sekhar Jena1, Suresh Sanda1

  • 1Department of Chemistry, IISER Bhopal, Bhopal By-pass Road, Bhauri, Bhopal - 462066, Madhya Pradesh (India).

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PubMed
Summary

Synthesized lanthanide-based coordination polymers exhibit magnetic refrigerant properties and humidity-dependent proton conductivity. These materials show potential for cryogenic applications and sensing technologies.

Keywords:
carboxylate ligandsconducting materialscoordination polymerslanthanidesmagneticproperties

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Area of Science:

  • Materials Science
  • Inorganic Chemistry
  • Crystallography

Background:

  • Lanthanide-based coordination polymers (CPs) are explored for their unique magnetic and conductive properties.
  • Developing novel CPs with tailored structures is crucial for advanced material applications.

Purpose of the Study:

  • To synthesize and characterize novel isostructural lanthanide-based 2D coordination polymers.
  • To investigate the magnetic properties, proton conductivity, and water adsorption behavior of these CPs.

Main Methods:

  • Single-crystal X-ray diffraction for structural analysis.
  • Magnetic property measurements (isothermal magnetization).
  • Impedance spectroscopy for proton conductivity and water-vapor adsorption studies.
  • Monte Carlo simulations for adsorption behavior.

Main Results:

  • Three isostructural 2D CPs {[Ln2(L)3(H2O)2]n⋅2nCH3OH)⋅2nH2O} (Ln=Gd, Tb, Dy) were synthesized and structurally elucidated.
  • Complex 1 (Gd) demonstrated ferromagnetic interactions and significant magnetic entropy change (-32.8 J kg⁻¹ K⁻¹ at 4 K), acting as a cryogenic magnetic refrigerant.
  • Complex 3 (Dy) exhibited slow relaxation of magnetization below 10 K.
  • All complexes displayed humidity-dependent proton conductivity (up to 1.1×10⁻³ S cm⁻¹) at elevated temperatures, retaining conductivity for 10 hours.
  • Water-vapor adsorption studies revealed high adsorption capacities and hysteretic behavior, with Monte Carlo simulations confirming preferential adsorption in interlayer spaces.

Conclusions:

  • The synthesized lanthanide-based CPs possess promising cryogenic magnetic refrigerant capabilities and humidity-sensitive proton conductivity.
  • The structural features, particularly the interlayer space, facilitate significant water adsorption and contribute to proton conductivity.
  • These materials hold potential for applications in magnetic refrigeration and humidity sensing.