Covert MOF-Based Photoluminescent Tags via Tunable Linker Energetics

Deneff, Jacob I.; Rohwer, Lauren S.; Butler, Kimberly S.; Valdez, Nichole R.; Rodriguez, Mark A.; Luk, Ting S.; Sava Gallis, Dorina F.

doi:10.1021/acsami.1c20432

Title: Covert MOF-Based Photoluminescent Tags via Tunable Linker Energetics

Journal Article · Fri Jan 07 00:00:00 EST 2022 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.1c20432· OSTI ID:1855802

Deneff, Jacob I. ^[1]; Rohwer, Lauren S. ^[1];

^[1]; Valdez, Nichole R. ^[1]; Rodriguez, Mark A. ^[1]; Luk, Ting S. ^[1];

^[1]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

We report that the optical anticounterfeiting tags utilize the photoluminescent properties of materials to encode unique patterns, enabling identification and validation of important items and assets. These tags must combine optical complexity with ease of production and authentication to both prevent counterfeiting and to remain practical for widespread use. Metal–organic frameworks (MOFs) based on polynuclear, rare earth clusters are ideal materials platforms for this purpose, combining fine control over structure and composition, with tunable, complex energy transfer mechanisms via both linker and metal components. Here we report the design and synthesis of a set of heterometallic MOFs based on combinations of Eu, Nd, and Yb with the tetratopic linker 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene. The energetics of this linker facilitate the intentional concealment of the visible emissions from Eu while retaining the infrared emissions of Nd and Yb, creating an optical tag with multiple covert elements. Unique to the materials system reported herein, we document the occurrence of a previously not observed 11-metal cluster correlated with the presence of Yb in the MOFs, coexisting with a commonly encountered 9-metal cluster. We demonstrate the utility of these materials as intricate optical tags with both rapid and in-depth screening techniques, utilizing orthogonal identifiers across composition, emission spectra, and emission decay dynamics. This work highlights the important effect of linker selection in controlling the resulting photoluminescent properties in MOFs and opens an avenue for the targeted design of highly complex, multifunctional optical tags.

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Research Organization:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC)

Grant/Contract Number:: NA0003525

OSTI ID:: 1855802

Report Number(s):: SAND2022-2535J; 703879

Journal Information:: ACS Applied Materials and Interfaces, Vol. 14, Issue 2; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Covert MOF-Based Photoluminescent Tags via Tunable Linker Energetics

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