Smaller than a nanoparticle with the design of discrete polynuclear molecular complexes displaying near-infrared to visible upconversion.

This work shows that the operation of near-infrared to visible light-upconversion in a discrete molecule is not limited to non-linear optical processes, but may result from superexcitation processes using linear optics. The design of nine-coordinate metallic sites made up of neutral N-heterocyclic donor atoms in kinetically inert dinuclear [GaEr(L1)(3)](6+) and trinuclear [GaErGa(L2)(3)](9+) helicates leads to [ErN(9)] chromophores displaying unprecedented dual visible nanosecond Er((4)S(3/2)→(4)I15/2) and near-infrared microsecond Er((4)I(13/2)→(4)I1(5/2)) emissive components. Attempts to induce one ion excited-state absorption (ESA) upconversion upon near-infrared excitation of these complexes failed because of the too-faint Er-centred absorption cross sections. The replacement of the trivalent gallium cation with a photophysically-tailored pseudo-octahedral [CrN(6)] chromophore working as a sensitizer for trivalent erbium in [CrEr(L1)(3)](6+) improves the near-infrared excitation efficiency, leading to the observation of a weak energy transfer upconversion (ETU). The connection of a second sensitizer in [CrErCr(L2)(3)](9+) generates a novel mechanism for upconversion, in which the superexcitation process is based on the Cr(III)-sensitizers. Two successive Cr→Er energy transfer processes (concerted-ETU) compete with a standard Er-centred ETU, and a gain in upconverted luminescence by a factor larger than statistical values is predicted and observed.