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We report the first proof of the ability of octahedral tungsten clusters to emit red–NIR light and to produce singlet oxygen upon two-photon absorption, in solution and in the solid-state. Such discoveries open new perspectives for tungsten cluster compounds in several fields like optoelectronics, photodynamic therapy, and bioimaging.

Graphical abstract: Evidencing ((n-C4H9)4N)2[W6I14] red–NIR emission and singlet oxygen generation by two photon absorption

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