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The combination of p-donating amido with p-
accepting pyridine coordination units in a tridentate chelate
ligand causes a strong nephelauxetic effect in a homoleptic CrIII
complex, which shifts its luminescence to the NIR-II spectral
range. Previously explored CrIII polypyridine complexes
typically emit between 727 and 778 nm (in the red to NIR-I
spectral region), and ligand design strategies have so far
concentrated on optimizing the ligand field strength. The
present work takes a fundamentally different approach and
focusses on increasing metal–ligand bond covalence to shift the
ruby-like 2E emission of CrIII to 1067 nm at 77 K.