Room-Temperature Upconversion in a Nanosized {Ln15} Molecular Cluster-Aggregate.

Abstract

The successive absorption of low-energy photons to the accumulation of the intermediate excited states leading to higher energy emission is still a challenge in molecular architectures. Contrary to low-phonon solids and nanoparticles, the rational construction of molecular systems containing an excess of donor atoms in relation to acceptor ones is far from trivial. Moreover, the vibrations caused by high-energy oscillators commonly present on coordination compounds result in serious drawbacks on molecular upconversion. To overcome these limitations, we demonstrate that upconversion can be achieved even at room temperatures through the use of molecular cluster-aggregates (MCAs). To achieve the upconverted emission, we synthesized a MCA containing 15 lanthanide ions, {Er2Yb13}, ensuring an excess of donor atoms. With the excitation on the ytterbium ion, the characteristic green and red emissions from erbium were obtained at room temperature. To prove the mechanism behind the upconversion process, four other compositions were synthesized and studied, namely, {Y13Er2}, {Y10Er5}, {Er10Yb5}, and {Y10Er1Yb4}. Upconversion quantum yield values on the order of 10-3% were obtained, values 100000 times higher than for previously reported lanthanide-based molecular upconverting systems. The presented methodology is an interesting approach to address a fine composition control and harness the upconversion properties of nanoscale molecular materials.