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

• Photosensitizers for sensitized triplet-triplet annihilation upconversion (sTTA-UC) often rely on precious heavy metals, whereas coordination complexes based on abundant first-row transition metals are less common. This is mainly because long-lived triplet excited states are more difficult to obtain for 3d metals, particularly when the d-subshell is only partially filled. Here, we report the first example of sTTA-UC based on a 3d6 metal photosensitizer yielding an upconversion performance competitive with precious metal-based analogues. Using a newly developed Cr0 photosensitizer featuring equally good photophysical properties as an OsII benchmark complex in combination with an acetylene-decorated anthracene annihilator, red-to-blue upconversion is achievable. The upconversion efficiency under optimized conditions is 1.8 %, and the excitation power density threshold to reach the strong annihilation limit is 5.9 W/cm2. These performance factors, along with high photostability, permit the initiation of acrylamide polymerization by red light, based on radiative energy transfer between delayed annihilator fluorescence and a blue light absorbing photo-initiator. Our study provides the proof-of-concept for photon upconversion with elusive first-row analogues of widely employed precious d6 metal photosensitizers, and for their application in photochemical reactions triggered by excitation wavelengths close to near-infrared.

Ämnesord

NATURVETENSKAP  -- Fysik -- Atom- och molekylfysik och optik (hsv//swe)

NATURAL SCIENCES  -- Physical Sciences -- Atom and Molecular Physics and Optics (hsv//eng)

NATURVETENSKAP  -- Kemi -- Teoretisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Theoretical Chemistry (hsv//eng)

Nyckelord

Chromium(0) Complex

Energy Transfer

Laser Spectroscopy

Polymerization

Sensitized Triplet-Triplet Annihilation Upconversion

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