Leveraging the redox activities of cerium and dibenzotetrathiafulvalene to discover a photo-responsive magnetic material

Abstract

Stimuli-responsive changes in lanthanide-based materials are a promising research direction. In this study, [DBTTF]₄[Ce₂Cl₁₀] DBTTF = dibenzotetrathiafulvalene (1) was synthesized by a light-induced crystallization, where photo-oxidation of DBTTF enables formation of the cerium dimer [Ce₂Cl₁₀]⁴⁻. Intermolecular interactions between the stacked organic units of the crystal result in charge transfer bands in the visible-NIR (near-infrared) region, evident in the solid-state absorption spectrum upon comparison with the solution spectrum. The assignments of the sublattice oxidation states were made with single-crystal X-ray diffraction (SC-XRD) structural characterization, Raman spectroscopy, X-ray absorption spectroscopy, and magnetometry. Continuous 532 nm laser irradiation of the microcrystalline solid modulates the redox states in 1, leading to ∼40% reduction in the observed magnetization at 2 K. Density functional theory PBE+U/HSE06 band structure calculations predict Mott insulating behavior in 1, with a bandgap of 0.54/0.81 eV, and further support the conjecture that the observed photo-induced change in magnetization results from electron transfer from the [Ce₂Cl₁₀]⁴⁻ anions to the π-stacked [DBTTF]₂²⁺ organic dimer subunits. An enhancement in conductivity is similarly observed upon 532 nm irradiation, determined by single-crystal transport measurements. The findings reveal that photo-responsive lanthanide-based materials can be achieved by integration of redox-active organic moieties with redox-active lanthanide cations for the realization of switchable, photo-magnetic materials.