Journal article
Molecular Origins of Near-Infrared Luminescence in Molybdenum and Tungsten Oxyhalide Perovskites
Chemistry of materials, Vol.36(16), pp.7754-7763
15 Aug 2024
PMID: 39220614
Featured in Collection : UN Sustainable Development Goals @ Drexel
Abstract
Materials with near-infrared (near-IR) luminescence are desirable for applications in communications and sensing, as well as biomedical diagnostics and imaging. The most used inorganic near-IR emitters rely on precise doping of host crystal structures with select rare-earth or transition metal ions. Recently, another class of materials with intrinsic near-IR emission has been reported. The compositions of these materials were initially described as vacancy-ordered halide double perovskites Cs2MoCl6 and Cs2WCl6, but further investigation by some of us on the compound reported as Cs2WCl6 revealed an oxyhalide instead, with a composition Cs2WOxCl6-x, where 1 < x < 2. Here we demonstrate that the Mo compounds similarly possess the composition Cs2MoOxCl6-x or Cs2MoOxBr6-x where 1 < x < 2. Preparing the pure halide appears harder for Mo than for W, and we have not succeeded in doing so. The distinctly different composition requires the coordination environment and oxidation state for the Mo and W centers to be reconsidered from what was assumed for the pure halides. In this work, we examine the mechanism for near-IR emission in these materials given their true structures and compositions. We demonstrate that the luminescence is due to the specific d-orbital splitting caused by the presence of oxygen in the distorted [MOX5](2-) octahedra (X is Cl or Br). The fine structure in the emission spectra at low temperatures has been resolved and is attributed to vibronic coupling to the Mo-O and W-O bond stretches. Understanding the true structure and composition of these interesting materials, besides explaining the near-IR luminescence, suggests how this desirable emission can be realized and manipulated.
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Details
- Title
- Molecular Origins of Near-Infrared Luminescence in Molybdenum and Tungsten Oxyhalide Perovskites
- Creators
- Emily E. Morgan - University of California, Santa BarbaraAlexandra Brumberg - University of California, Santa BarbaraShobhana Panuganti - Northwestern UniversityGreggory T. Kent - University of California, Santa BarbaraArava Zohar - University of California, Santa BarbaraAlexander A. Mikhailovsky - University of California, Santa BarbaraMercouri G. Kanatzidis - Northwestern UniversityRichard D. Schaller - Northwestern UniversityMichael L. Chabinyc - University of California, Santa BarbaraAnthony K. Cheetham - University of California, Santa BarbaraRam Seshadri - University of California, Santa BarbaraArgonne National Laboratory (ANL), Argonne, IL (United States)
- Publication Details
- Chemistry of materials, Vol.36(16), pp.7754-7763
- Publisher
- Amer Chemical Soc
- Number of pages
- 10
- Grant note
- DMR-2308708 / NSF; National Science Foundation (NSF) University of California, Santa Barbara; University of California System DE-SC0024422 / U.S. Department of Energy (DOE); United States Department of Energy (DOE) Ras Al Khaimah Center for Advanced Materials DGE-1842165 / National Science Foundation Graduate Research Fellowship Program; National Science Foundation (NSF) 66886LSRIP / DoD ARO DURIP Elings Postdoctoral Fellowship Program DE-SC0024422; DE-AC02-06CH11357 / U.S. Department of Energy; United States Department of Energy (DOE) 2139319 / NSF Graduate Research Fellowship Program; National Science Foundation (NSF) CHE-1808590 / National Science Foundation MSN
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Chemistry
- Web of Science ID
- WOS:001292264500001
- Scopus ID
- 2-s2.0-85201451570
- Other Identifier
- 991022053793104721
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- Collaboration types
- Domestic collaboration
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- Web of Science research areas
- Chemistry, Physical
- Materials Science, Multidisciplinary