Mixed-Metal and Mixed-Ligand Lanthanide Metal-Organic Frameworks Based on 2,6-Naphthalenedicarboxylate: Thermally Activated Sensitization and White-Light Emission.

Abstract

Trivalent lanthanide ions (Ln3+) hold an exceptional position in the field of optoelectronic materials due to their atomic-like emission spectra and long luminescence lifetimes. Metal-organic frameworks (MOFs) and coordination polymers are particularly suited as luminescent materials due to their structural diversity and ease of functionalization both at bridging ligands and/or metal centers. In this contribution, we present a series of mixed-metal Ln3+/Eu3+ (Ln = La, Gd) and mixed-ligand (2,6-naphthalenedicarboxylate (ndc2-) and 4-aminonaphthalene-2,6-dicarboxylate (andc2-)) MOFs belonging to three different structural types, with emissions spanning most of the visible region, thereby constituting favorable materials for color tuning and white-light emission. We investigate the thermal stability and photophysical properties of the synthesized materials with regard to their metal and ligand doping levels and structural type, where we discuss excimer and monomer emission. The photophysical study, involving both steady-state and time-resolved luminescence measurements, allows us to discuss the possible energy migration and Eu3+ sensitization pathways that take place within these materials following ligand excitation. Low-temperature luminescence studies led us to determine the energies of the ligand-based excited states and investigate their participation in thermally activated energy transfer mechanisms within the studied lattices. We observe emission quantum yields of up to 87% for the Eu3+-doped materials, while their ligand- and metal-doped counterparts show decreased quantum yields of up to 17%. Finally, we attempt fine color tuning by carefully adjusting the doping levels to achieve yellow and white-light emission.