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The protons in unsubstituted alkanes are strongly shielded with chemical shifts below 1.8 ppm. Methine, methylene, and methyl protons appear at approximately 1.7, 1.2 and 0.7 ppm, while the proton signal from methane appears at 0.23 ppm. An electronegative substituent, such as chlorine, withdraws the electron density from the protons, increasing their chemical shift. Progressive substitution of the hydrogens in methane by chlorine shifts the proton signals increasingly downfield, to 3.05 ppm in...
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Clusterization-Induced Emission Shift in Copper(I) Thiones.

Bikash Lahkar1, Dinesh Harijan1, Gopendra Muduli1

  • 1Organometallics and Materials Chemistry Lab, Department of Chemistry, Indian Institute of Technology Hyderabad, Kandi, Sangareddy, Telangana 502285, India.

The Journal of Physical Chemistry Letters
|December 26, 2025
PubMed
Summary
This summary is machine-generated.

New copper clusters exhibit unique luminescence for light-emitting applications. These materials show tunable optical properties and potential for use in LEDs.

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Area of Science:

  • Materials Science
  • Inorganic Chemistry
  • Photophysics

Background:

  • Cluster-induced luminescence is crucial for advanced light-emitting applications.
  • Copper clusters are promising luminogens due to their unique electronic and optical properties.

Purpose of the Study:

  • To synthesize and characterize novel copper clusters with tunable emissive properties.
  • To investigate the structural, optical, and electronic characteristics of these clusters.
  • To evaluate their potential for use in light-emitting diode (LED) applications.

Main Methods:

  • Synthesis of two distinct copper clusters: [(L)Cu(μ2-I)]2 (1) and a cocluster [(L)Cu(μ2-I)]2·[(μ2-L)Cu2(μ2-I)(μ3-I)]2 (2).
  • Characterization using X-ray crystallography, UV-Vis spectroscopy, and photoluminescence spectroscopy.
  • Optical band gap determination via Tauc plots.
  • Computational analysis using Density Functional Theory (DFT) and Time-Dependent DFT (TD-DFT).
  • Coating clusters onto 3V LEDs to assess performance.

Main Results:

  • Two novel copper clusters, 1 and 2, were successfully synthesized and structurally characterized.
  • Cluster 2 exhibited a redshift of 55 nm in crystalline emission compared to cluster 1, attributed to crystal packing and noncovalent interactions.
  • Optical band gaps were calculated as 2.40 eV for 1 and 2.45 eV for 2.
  • DFT calculations showed HOMO-LUMO energy gaps of 3.03 eV for 1 and 2.75 eV for 2.
  • TD-DFT revealed emission arises from 3XLCT, 3MLCT, and 3ILCT transitions.
  • LEDs coated with clusters showed emissions similar to the pure crystalline samples.

Conclusions:

  • The synthesized copper clusters demonstrate tunable luminescence and unique emissive properties.
  • Crystal packing significantly influences the solid-state emission characteristics.
  • The electronic structure and emission mechanisms were elucidated through computational studies.
  • These copper clusters show promise for integration into practical LED devices.