Distortion Engineering: A Strategy to Modulate Molecular Upconversion with Molecular Cluster-Aggregates

The rational engineering of molecules is a powerful chemistry tool of pivotal importance in the fields of molecular magnetism and luminescence. Hence, systems that can be modulated via molecular engineering and composition control are expected to present extra versatility regarding the tunability of their properties. This is the case with molecular cluster aggregates (MCAs), high nuclearity molecular compounds. Herein, we demonstrate how the union of both strategies, namely, composition control and molecular engineering, can be employed to enhance molecular upconversion in MCAs. This was achieved by doping a {GdErYb} MCA with Ce^III ions. By replacement of the optically silent Gd^III ions with Ce^III, the upconversion mechanism is modified due to Ce^III-mediated cross-relaxation. In addition to this effect, we could also engineer the degree of metal site distortion due to the larger size of Ce^III ions, relaxing the selection rules and impacting the upconversion quantum yield and luminescent thermometry. Opto-structural correlations demonstrate that the presented molecular engineering strategy can be used to enhance the performance of molecular upconverters.