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

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 Os^II 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.