Controlling Ligand Excimer Formation with Dipole Changes in Emissive Rare-Earth/Phosphonic Acid Complexes

Johnson, Justin C.; Larsen, Ross E.; Douair, Iskander; Kuvayskaya, Anastasia; Sellinger, Alan; Ferguson, Andrew

doi:10.1021/acsomega.5c08830

Title: Controlling Ligand Excimer Formation with Dipole Changes in Emissive Rare-Earth/Phosphonic Acid Complexes

Journal Article · Wed Sep 24 00:00:00 UTC 2025 · ACS Omega

DOI: https://doi.org/10.1021/acsomega.5c08830 · OSTI ID:3013237

^[1];

^[1]; Douair, Iskander ^[2]; Kuvayskaya, Anastasia ^[3];

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^[1]

National Renewable Energy Laboratory (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States). Renewable and Sustainable Energy Institute (RSEI)
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Colorado School of Mines, Golden, CO (United States)

The interactions between substituted arylvinyl phosphonic acid (AVPA) ligands within a Eu-AVPA complex are shown to influence the outcomes of excited state evolution after photoexcitation. Compared with unfunctionalized AVPAs, pairs of ligands functionalized with CF₃ in the para position preassociate in the ground state of complexes with Eu³⁺ according to calculated geometry optimizations. The CF₃-substituted AVPA complexes show evidence of red-shifted optical absorption and undergo more efficient excimer formation, as revealed by transient absorption spectroscopy. We rationalize this behavior through simulations of excited-state geometry optimizations that reveal evolution toward interligand phenyl-phenyl planarity for specific excited states. Emission from complexed Eu³⁺ after energy transfer from the ligand is found to be weaker with CF₃ substitution, which we hypothesize is due to intracomplex, interligand aggregates with excimer-promoting geometries. These observations point to the need to consider ground-state geometries as well as dynamic excited-state processes to understand the flow of energy in rare earth coordination complexes.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 3013237

Report Number(s):: NREL/JA--5900-95546

Journal Information:: ACS Omega, Journal Name: ACS Omega Journal Issue: 39 Vol. 10; ISSN 2470-1343

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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09 BIOMASS FUELS
36 MATERIALS SCIENCE
excimer
ligand
photoluminescence
rare earth
separation

Title: Controlling Ligand Excimer Formation with Dipole Changes in Emissive Rare-Earth/Phosphonic Acid Complexes

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