Composition Control in Molecular Cluster-Aggregates: A Toolbox for Optical Output Tunability via Energy Transfer Pathways

• Published in: ACS applied materials & interfaces Vol. 15; no. 37; pp. 44137 - 44146
• Main Authors: Calado, Claudia M. S., Gálico, Diogo A., Murugesu, Muralee
• Format: Journal Article
• Language: English
• Published: American Chemical Society 20-09-2023
• Subjects: Functional Nanostructured Materials (including low-D carbon); energy transfer; molecular cluster-aggregates; composition control; optical thermometry; lanthanides
• ISSN: 1944-8244; 1944-8252
• DOI: 10.1021/acsami.3c10648

Composition control is a powerful tool for obtaining high-performance lanthanide (Ln) luminescent materials with adjustable optical outputs. This strategy is well-established for hierarchically structured nanoparticles, but it is rarely applied to molecular compounds due to the limited number of metal centers within a single unit. In this work, we present a series of molecular cluster-aggregates (MCAs) with an icosanuclear core {Ln2Eu2Tb16} (Ln = Ce, Pr, Nd, Sm, Gd, Dy, Ho, Er, Tm, and Yb) in which we explore composition control, akin to nanoparticles, to modulate the optical output. More specifically, we target to understand how the presence of a third LnIII doping ion would impact the well-known TbIII → EuIII energy transfer and the ratiometric optical thermometry performance based on the TbIII/EuIII pair. Photophysical properties at room and at varying temperatures were investigated. Based on experimental data and well-established intrinsic features, such as spin–orbit coupling strength and LnIII 4f energy levels’ structure, we discuss the possible luminescent processes present in each MCA and provide insight into qualitative trends that can be rationally correlated throughout the series.