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Ionic Bonding and Electron Transfer02:48

Ionic Bonding and Electron Transfer

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Ions are atoms or molecules bearing an electrical charge. A cation (a positive ion) forms when a neutral atom loses one or more electrons from its valence shell, and an anion (a negative ion) forms when a neutral atom gains one or more electrons in its valence shell. Compounds composed of ions are called ionic compounds (or salts), and their constituent ions are held together by ionic bonds: electrostatic forces of attraction between oppositely charged cations and anions. 
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Alkyl Halides02:45

Alkyl Halides

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Structural Properties
Alkyl halides are halogen-substituted alkanes wherein one or more hydrogen atoms of an alkane is replaced by a halogen atom such as fluorine, chlorine, bromine, or iodine. The carbon atom in an alkyl halide is bonded to the halogen atom, which is sp3-hybridized and exhibits a tetrahedral shape.
Unlike alkyl halides, compounds in which a halogen atom is bonded to an sp2 -hybridized carbon atom of a carbon-carbon double bond (C=C) are called vinyl halides. Whereas aryl...
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Mass Spectrometry: Alkyl Halide Fragmentation01:22

Mass Spectrometry: Alkyl Halide Fragmentation

1.0K
Chlorine isotopes exist as 35Cl and 37Cl in a 3:1 ratio, while bromine isotopes exist as 79Br and 81Br in a 1:1 ratio. The mass spectrum of alkyl halides typically produces two distinct molecular ion peaks, the molecular ion peak, [M], and the molecular ion plus two, [M + 2] peak. The relative heights of these two peaks are proportional to the isotopic abundance ratios of the halide. For example, 2‐chloropropane and 1‐bromopropane display two peaks with relative peak heights in a 3:1 and...
1.0K
Trends in Lattice Energy: Ion Size and Charge02:54

Trends in Lattice Energy: Ion Size and Charge

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An ionic compound is stable because of the electrostatic attraction between its positive and negative ions. The lattice energy of a compound is a measure of the strength of this attraction. The lattice energy (ΔHlattice) of an ionic compound is defined as the energy required to separate one mole of the solid into its component gaseous ions. For the ionic solid sodium chloride, the lattice energy is the enthalpy change of the process:
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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 the dxy,...
41.8K
Ionic Crystal Structures02:42

Ionic Crystal Structures

14.2K
Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...
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Periodic Trends in Intra-ionic Excited State Quenching by Halide.

Matthew J Goodwin1, Alexander M Deetz1, Paul J Griffin1

  • 1Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States.

Inorganic Chemistry
|August 9, 2024
PubMed
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Noncovalent interactions stabilize reactants, significantly impacting photoinitiated electron transfer. A novel iridium photocatalyst shows halide reactivity trends, influenced by halide size and electron affinity.

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Area of Science:

  • Photochemistry
  • Inorganic Chemistry
  • Physical Chemistry

Background:

  • Noncovalent interactions influence excited-state reactivity in photoinitiated redox reactions.
  • Stabilization of associated species affects the kinetics and thermodynamics of photoinitiated electron transfer.

Purpose of the Study:

  • To investigate the reactivity of a novel iridium(III) photocatalyst with halides (iodide, bromide, chloride).
  • To explore the impact of noncovalent interactions on photoredox behavior and electron transfer dynamics.

Main Methods:

  • Synthesis of an iridium(III) photocatalyst with an anion-sensitive, amide-substituted bipyridine ligand.
  • Studying photocatalyst reactivity with halides in acetonitrile (polar) and dichloromethane (nonpolar) solvents.
  • Analysis of binding affinities, quenching mechanisms (static and dynamic), and photophysical properties.

Main Results:

  • A periodic trend in halide binding affinity was observed, increasing with decreasing ionic radius (Keq from ~10^3 to >10^6) in polar media.
  • Stoichiometric association was observed for all halides in nonpolar media.
  • Static quenching was evident for iodide and bromide, while dynamic quenching occurred with all halides.

Conclusions:

  • Preassociation of quenchers via hydrogen bonding significantly impacts halide adduct photophysics.
  • The thermodynamics of intra-ionic photo-oxidation are modulated by noncovalent interactions.
  • Halide size and electron affinity are critical factors determining photoredox behavior.