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Photoluminescent Linear Carbene-Silver-Amide Complexes.

Tanu Sharma1, Nirbhay Thakur1, Nitish Kumar1

  • 1Indian Institute of Technology Mandi, Mandi, Himachal Pradesh 175075, India.

Inorganic Chemistry
|July 28, 2025
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Summary

This study introduces novel linear carbene-silver-amide (CMA) complexes with N-heterocyclic carbene ligands, revealing their fluorescent properties. Complexes with electron-donating groups exhibit higher quantum yields, offering potential for advanced optical materials.

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Area of Science:

  • Organometallic Chemistry
  • Photophysics
  • Materials Science

Background:

  • Carbene-metal-amide (CMA) complexes, particularly with cyclic (alkyl)(amino)carbenes (CAACs) and copper or gold, are known for their photophysical properties.
  • Research on CMA complexes involving classical N-heterocyclic carbene (NHC) ligands and silver(I) for photophysical studies is limited.

Purpose of the Study:

  • To synthesize and characterize novel linear carbene-silver-amide complexes using NHC ligands.
  • To investigate the photophysical properties, including UV-visible absorption and luminescence, of these silver(I) complexes.
  • To correlate structural features, specifically substituents on the carbazolide ligand, with observed photophysical behavior.

Main Methods:

  • Synthesis and characterization of five linear carbene-silver-amide complexes using various NHC and carbazolide ligands.
  • Spectroscopic characterization including 1H, 13C{1H}, and 2D NMR, and high-resolution mass spectrometry.
  • Single-crystal X-ray diffraction analysis for one complex.
  • UV-visible absorption and luminescence spectroscopy to determine photophysical properties like emission wavelength, excited state lifetime, and quantum yield.

Main Results:

  • Five novel linear carbene-silver-amide complexes were successfully synthesized and characterized.
  • The complexes exhibit UV-visible absorption up to 400 nm and photoluminescence between 360-430 nm in solution.
  • Luminescence originates from ligand-centered π-π* transitions and is fluorescent, with excited state lifetimes ranging from 1.3 to 7.8 ns.
  • Fluorescence quantum yields varied from 6.7% to 33.2%, with higher yields observed for complexes containing carbazolide units or electron-donating groups on the carbazolide.

Conclusions:

  • The synthesized linear carbene-silver-amide complexes display tunable fluorescent properties.
  • The presence of electron-donating groups on the carbazolide ligand enhances fluorescence quantum yields, suggesting potential applications in optoelectronics.
  • These findings expand the scope of studied CMA complexes and highlight silver(I) as a viable metal center for developing luminescent materials.