Leveraging the redox activities of cerium and dibenzotetrathiafulvalene to discover a photo-responsive magnetic material
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- University of Pennsylvania, Philadelphia, PA (United States)
- University at Buffalo, State University of New York, NY (United States)
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- École Polytechnique Fédérale de Lausanne (EPFL), Lausanne (Switzerland)
- University of Pennsylvania, Philadelphia, PA (United States); Department of Earth and Environmental Science (United States)
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.
- Research Organization:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University at Buffalo, State University of New York, NY (United States); University of Pennsylvania, Philadelphia, PA (United States); École Polytechnique Fédérale de Lausanne (EPFL), Lausanne (Switzerland)
- Sponsoring Organization:
- US Department of Energy; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences & Biosciences Division (SC-22.1); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
- Grant/Contract Number:
- AC02-05CH11231; SC0020169
- OSTI ID:
- 3367416
- Report Number(s):
- DOE-EJS-20169
- Journal Information:
- Chemical Science, Journal Name: Chemical Science Journal Issue: 18 Vol. 17; ISSN 2041-6539; ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry (RSC)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
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