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π Electron Effects on Chemical Shift: Overview

An applied magnetic field causes loosely bound π-electrons in organic molecules to circulate, producing a local or induced diamagnetic field over a large spatial volume. As the molecules tumble in solution, the field generated by π-electrons in spherical substituents results in a zero net field. However, the net field generated by π-electrons in non-spherical substituents is not zero. The effect of this induced field depends on the orientation of the molecule with respect to B0, resulting in...
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Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F&#8722;
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Bond evolution in electron transfer: a time-resolved EXAFS study.

Jie Chen1, Hua Zhang, Peter M Rentzepis

  • 1Department of Chemistry, University of California, Irvine, California 92697, USA.

The Journal of Physical Chemistry. A
|February 10, 2010
PubMed
Summary
This summary is machine-generated.

Photoinduced electron transfer in cobalt complexes was studied. Cobalt-nitrogen bonds rapidly changed length, indicating electron transfer from ligand to cobalt within 2 picoseconds.

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Area of Science:

  • Photochemistry
  • Inorganic Chemistry
  • Spectroscopy

Background:

  • Cobalt complexes are crucial in various chemical reactions.
  • Understanding photoinduced electron transfer is key to developing new materials and catalysts.

Purpose of the Study:

  • To investigate the photochemical mechanism of electron transfer in the [Co(III)(NH3)6](3+) complex.
  • To determine the kinetics and structural changes during the photoinduced redox reaction.

Main Methods:

  • Ultrafast Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy.
  • Optical transient spectroscopy.
  • Density Functional Theory (DFT) calculations.

Main Results:

  • The Cobalt-Nitrogen (Co-N) bond length increased from 1.93 Å to 2.12 Å within 2 picoseconds (ps) after excitation.
  • Spectra and kinetics indicate intramolecular electron transfer from ligand to cobalt.
  • Low quantum yield electron photodetachment was observed.

Conclusions:

  • The study elucidates the ultrafast photochemical mechanism of the Co(III) to Co(II) redox reaction.
  • The findings provide insights into the dynamics of electron transfer in coordination complexes.