Efficient Triplet-Triplet Annihilation Upconversion Sensitized by a Chromium(III) Complex via an Underexplored Energy Transfer Mechanism

Sensitized triplet-triplet annihilation upconversion (sTTA-UC) mainly relies on precious metal complexes thanks to their high intersystem crossing (ISC) efficiencies, excited state energies, and lifetimes, while complexes of abundant first-row transition metals are only rarely utilized and with often moderate UC quantum yields. [Cr(bpmp)(2)](3+) (bpmp=2,6-bis(2-pyridylmethyl)pyridine) containing earth-abundant chromium possesses an absorption band suitable for green light excitation, a doublet excited state energy matching the triplet energy of 9,10-diphenyl anthracene (DPA), a close to millisecond excited state lifetime, and high photostability. Combined ISC and doublet-triplet energy transfer from excited [Cr(bpmp)(2)](3+) to DPA gives (3)DPA with close-to-unity quantum yield. TTA of (3)DPA furnishes green-to-blue UC with a quantum yield of 12.0 % (close to the theoretical maximum). Sterically less-hindered anthracenes undergo a [4+4] cycloaddition with [Cr(bpmp)(2)](3+) and green light.

Automated summary

This study achieved efficient green-to-blue upconversion by using the earth-abundant chromium complex [Cr(bpmp)(2)](3+), with a quantum yield close to the theoretical maximum, showing potential for practical applications.