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First-Row d6 Metal Complex Enables Photon Upconversion and Initiates Blue Light-Dependent Polymerization with Red

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This study introduces a novel chromium-based photosensitizer for efficient triplet-triplet annihilation upconversion (sTTA-UC). This breakthrough enables red-to-blue light conversion using abundant metals, paving the way for new photochemical applications.

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Area of Science:

  • Photochemistry
  • Materials Science
  • Supramolecular Chemistry

Background:

  • Triplet-triplet annihilation upconversion (sTTA-UC) typically utilizes precious heavy metal photosensitizers.
  • Achieving long-lived triplet excited states in first-row transition metals (3d metals) for sTTA-UC is challenging, especially with partially filled d-subshells.

Purpose of the Study:

  • To demonstrate the first example of sTTA-UC using a 3d6 metal photosensitizer.
  • To develop a photosensitizer with performance competitive with precious metal analogues.
  • To explore applications in red-light-initiated photochemistry.

Main Methods:

  • Synthesis of a new chromium(0) photosensitizer.
  • Combination with an acetylene-decorated anthracene annihilator for red-to-blue upconversion.
  • Characterization of photophysical properties, including upconversion efficiency and excitation power density threshold.
  • Demonstration of acrylamide polymerization initiated by red light.

Main Results:

  • Achieved red-to-blue upconversion with a Cr(0) photosensitizer and anthracene derivative.
  • Obtained an upconversion efficiency of 1.8% under optimized conditions.
  • Determined an excitation power density threshold of 5.9 W/cm² for strong annihilation.
  • Demonstrated high photostability of the system.
  • Successfully initiated acrylamide polymerization using red light.

Conclusions:

  • Proof-of-concept for photon upconversion using first-row transition metal analogues of precious d6 metal photosensitizers.
  • Potential for photochemical reactions triggered by near-infrared excitation wavelengths.
  • Opens avenues for developing cost-effective and sustainable upconversion systems.