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Related Concept Videos

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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Hydrogen Bonds00:26

Hydrogen Bonds

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Hydrogen bonds are weak attractions between atoms that have formed other chemical bonds. One of these atoms is electronegative, like oxygen, and has a partial negative charge. The other is a hydrogen atom that has bonded with another electronegative atom and has a partial positive charge.
Hydrogen Bonds Control the World!
Because hydrogen has very weak electronegativity when it binds with a strongly electronegative atom, such as oxygen or nitrogen, electrons in the bond are unequally shared....
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Hydrogen Bonds01:04

Hydrogen Bonds

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A hydrogen bond is formed when a weakly positive hydrogen atom already bonded to one electronegative atom (for example, the oxygen in the water molecule) is attracted to another electronegative atom from another polar molecule, such as water (H2O), hydrogen fluoride (HF), or ammonia (NH3). The huge electronegativity difference between the H atom (2.1) and the atom to which it is bonded (4.0 for an F atom, 3.5 for an O atom, or 3.0 for an N atom), combined with the very small size of an H atom...
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Spin–Spin Coupling: One-Bond Coupling01:17

Spin–Spin Coupling: One-Bond Coupling

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Coupling interactions are strongest between NMR-active nuclei bonded to each other, where spin information can be transmitted directly through the pair of bonding electrons. While nuclei polarize their electrons to the opposite spins, the bonding electron pair has opposite spins. Configurations with antiparallel nuclear spins are expected to be lower in energy. When coupling makes antiparallel states more favorable, J is considered to have a positive value. The one-bond coupling constant, 1J,...
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Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)01:20

Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)

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Two NMR-active nuclei bonded to a central atom can be involved in geminal or two-bond coupling. Geminal coupling is commonly seen between diastereotopic protons in chiral molecules and unsymmetrical alkenes, among others.
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
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Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)01:22

Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)

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Vicinal or three-bond coupling is commonly observed between protons attached to adjacent carbons. Here, nuclear spin information is primarily transferred via electron spin interactions between adjacent C‑H bond orbitals. This generally favors the antiparallel arrangement of spins, so 3J values are usually positive.
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the involved orbitals. The...
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Isotopic Effect in Double Proton Transfer Process of Porphycene Investigated by Enhanced QM/MM Method
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Efficient electron transfer across hydrogen bond interfaces by proton-coupled and -uncoupled pathways.

Tao Cheng1, Dong Xue Shen1, Miao Meng1

  • 1Department of Chemistry, Jinan University, 601 Huang-Pu Avenue West, 510632, Guangzhou, China.

Nature Communications
|April 6, 2019
PubMed
Summary

Electron transfer through hydrogen bonds was studied. Researchers found it can occur via proton-coupled or proton-uncoupled pathways, offering insights into biological charge transport.

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Area of Science:

  • Chemistry
  • Physical Chemistry
  • Supramolecular Chemistry

Background:

  • Electron transfer is crucial in chemical and biological processes.
  • Hydrogen bonds are fundamental in molecular interactions.
  • Electron transfer through hydrogen bonds is an understudied area.

Purpose of the Study:

  • To investigate thermal electron transfer through amide-amide hydrogen bonded interfaces.
  • To explore the mechanisms and efficiencies of electron transfer across hydrogen bonds.
  • To understand the role of electronic coupling and hydrogen bond strength in electron transfer pathways.

Main Methods:

  • Synthesis of mixed-valence complexes with Mo2 units.
  • Optical spectroscopy for electron transfer rate determination.
  • Marcus-Hush theory and vibrational band broadening simulations.

Main Results:

  • Electron transfer rates through dual hydrogen bonds are on the order of ~10^10 s^-1.
  • Electron transfer efficiencies are comparable to π-conjugated systems.
  • Two distinct pathways were identified: proton-coupled and proton-uncoupled.

Conclusions:

  • Electron transfer across hydrogen bonds can occur via proton-coupled and proton-uncoupled mechanisms.
  • A mechanistic switch between pathways is achievable by tuning electronic coupling and hydrogen bonding.
  • Findings illuminate charge and energy transport in biological systems.