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

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.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA); 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, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 2 Vol. 14; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (49)

Visible-Light Excited Luminescent Thermometer Based on Single Lanthanide Organic Frameworks Li, Liang; Zhu, Yali; Zhou, Xinhui Advanced Functional Materials, Vol. 26, Issue 47 https://doi.org/10.1002/adfm.201603179	journal	October 2016
An Advanced Tunable Multimodal Luminescent La ₄ GeO ₈ : Eu ²⁺ , Er ³⁺ Phosphor for Multicolor Anticounterfeiting Pei, Pengxiang; Wei, Ruiping; Wang, Binbin Advanced Functional Materials, Vol. 31, Issue 31 https://doi.org/10.1002/adfm.202102479	journal	May 2021
Tuning the Dual Emission of Photon-Upconverting Nanoparticles for Ratiometric Multiplexed Encoding Gorris, Hans H.; Ali, Reham; Saleh, Sayed M. Advanced Materials, Vol. 23, Issue 14 https://doi.org/10.1002/adma.201004697	journal	February 2011
Optical Nanomaterials and Enabling Technologies for High‐Security‐Level Anticounterfeiting Ren, Wei; Lin, Gungun; Clarke, Christian Advanced Materials https://doi.org/10.1002/adma.201901430	journal	June 2019
Triple-Mode Emission of Carbon Dots: Applications for Advanced Anti-Counterfeiting Jiang, Kai; Zhang, Ling; Lu, Junfeng Angewandte Chemie International Edition, Vol. 55, Issue 25 https://doi.org/10.1002/anie.201602445	journal	May 2016
Host Differential Sensitization toward Color/Lifetime‐Tuned Lanthanide Coordination Polymers for Optical Multiplexing Ou, Yiyi; Zhou, Weijie; Zhu, Zece Angewandte Chemie International Edition, Vol. 59, Issue 52 https://doi.org/10.1002/anie.202011559	journal	October 2020
Encoding Multilayer Complexity in Anti‐Counterfeiting Heterometallic MOF‐Based Optical Tags Deneff, Jacob I.; Butler, Kimberly S.; Rohwer, Lauren E. S. Angewandte Chemie International Edition, Vol. 60, Issue 3 https://doi.org/10.1002/anie.202013012	journal	December 2020
Lanthanide Organic Framework Luminescent Thermometers Rocha, João; Brites, Carlos D. S.; Carlos, Luís D. Chemistry - A European Journal, Vol. 22, Issue 42 https://doi.org/10.1002/chem.201600860	journal	August 2016
Correlation between the lowest triplet state energy level of the ligand and lanthanide(III) luminescence quantum yield Latva, Martti; Takalo, Harri; Mukkala, Veli-Matti Journal of Luminescence, Vol. 75, Issue 2 https://doi.org/10.1016/S0022-2313(97)00113-0	journal	September 1997
Design of luminescent lanthanide complexes: From molecules to highly efficient photo-emitting materials Armelao, L.; Quici, S.; Barigelletti, F. Coordination Chemistry Reviews, Vol. 254, Issue 5-6 https://doi.org/10.1016/j.ccr.2009.07.025	journal	March 2010
Interface construction in microporous metal–organic frameworks from luminescent terbium-based building blocks Ning, Erlong; Yang, Lingyi; Tu, Binbin Journal of Colloid and Interface Science, Vol. 552 https://doi.org/10.1016/j.jcis.2019.05.056	journal	September 2019
Luminophoric organic molecules for anticounterfeit printing ink applications: an up-to-date review Muthamma, K.; Sunil, D.; Shetty, P. Materials Today Chemistry, Vol. 18 https://doi.org/10.1016/j.mtchem.2020.100361	journal	December 2020
A Long Journey in Lanthanide Chemistry: From Fundamental Crystallogenesis Studies to Commercial Anticounterfeiting Taggants Guillou, Olivier; Daiguebonne, Carole; Calvez, Guillaume Accounts of Chemical Research, Vol. 49, Issue 5 https://doi.org/10.1021/acs.accounts.6b00058	journal	April 2016
Building a shp : A Rare-Earth Metal–Organic Framework and Its Application in a Catalytic Photooxidation Reaction Quezada-Novoa, Victor; Titi, Hatem M.; Sarjeant, Amy A. Chemistry of Materials, Vol. 33, Issue 11 https://doi.org/10.1021/acs.chemmater.1c00917	journal	May 2021
Multi-Emissive Lanthanide-Based Coordination Polymers for Potential Application as Luminescent Bar-Codes Wang, Jinzeng; Suffren, Yan; Daiguebonne, Carole Inorganic Chemistry, Vol. 58, Issue 4 https://doi.org/10.1021/acs.inorgchem.8b03277	journal	February 2019
Antibody Targeted Metal–Organic Frameworks for Bioimaging Applications Butler, Kimberly S.; Pearce, Charles J.; Nail, Elizabeth A. ACS Applied Materials & Interfaces, Vol. 12, Issue 28 https://doi.org/10.1021/acsami.0c07835	journal	June 2020
Rapid Visual Authentication Based on DNA Strand Displacement Berk, Kimberly L.; Blum, Steven M.; Funk, Vanessa L. ACS Applied Materials & Interfaces, Vol. 13, Issue 16 https://doi.org/10.1021/acsami.1c02429	journal	April 2021
Inside-Out/Outside-In Tunability in Nanosized Lanthanide-Based Molecular Cluster-Aggregates: Modulating the Luminescence Thermometry Performance via Composition Control Gálico, Diogo A.; Murugesu, Muralee ACS Applied Materials & Interfaces, Vol. 13, Issue 39 https://doi.org/10.1021/acsami.1c13684	journal	September 2021
Hybrid Plasmonic/Photonic Nanoscale Strategy for Multilevel Anticounterfeit Labels Caligiuri, Vincenzo; Patra, Aniket; De Santo, Maria P. ACS Applied Materials & Interfaces, Vol. 13, Issue 41 https://doi.org/10.1021/acsami.1c13701	journal	October 2021
Multifunctional, Tunable Metal–Organic Framework Materials Platform for Bioimaging Applications Sava Gallis, Dorina F.; Rohwer, Lauren E. S.; Rodriguez, Mark A. ACS Applied Materials & Interfaces, Vol. 9, Issue 27 https://doi.org/10.1021/acsami.7b05859	journal	June 2017
Carbon Dot Fluorescence-Lifetime-Encoded Anti-Counterfeiting Kalytchuk, Sergii; Wang, Yu; Poláková, Kateřina ACS Applied Materials & Interfaces, Vol. 10, Issue 35 https://doi.org/10.1021/acsami.8b11663	journal	August 2018
Excitation Wavelength-Dependent Dual-Mode Luminescence Emission for Dynamic Multicolor Anticounterfeiting Shi, Chen; Shen, Xiuyu; Zhu, Yanan ACS Applied Materials & Interfaces, Vol. 11, Issue 20 https://doi.org/10.1021/acsami.9b04213	journal	May 2019
Luminescent Supraparticles Based on CaF ₂ –Nanoparticle Building Blocks as Code Objects with Unique IDs Miller, Franziska; Wintzheimer, Susanne; Reuter, Tim ACS Applied Nano Materials, Vol. 3, Issue 1 https://doi.org/10.1021/acsanm.9b02245	journal	December 2019
The Extent of Pyrene Excimer Fluorescence Emission Is a Reflector of Distance and Flexibility: Analysis of the Segment Linking the LDL Receptor-Binding and Tetramerization Domains of Apolipoprotein E3 Bains, Gursharan K.; Kim, Sea H.; Sorin, Eric J. Biochemistry, Vol. 51, Issue 31 https://doi.org/10.1021/bi3005285	journal	July 2012
Tuning the Triplet Energy Levels of Pyrazolone Ligands to Match the ⁵ D ₀ Level of Europium(III) Shi, Mei; Li, Fuyou; Yi, Tao Inorganic Chemistry, Vol. 44, Issue 24 https://doi.org/10.1021/ic050844p	journal	November 2005
Efficient Sensitization of Europium, Ytterbium, and Neodymium Functionalized Tris-Dipicolinate Lanthanide Complexes through Tunable Charge-Transfer Excited States D’Aléo, Anthony; Picot, Alexandre; Beeby, Andrew Inorganic Chemistry, Vol. 47, Issue 22 https://doi.org/10.1021/ic8012969	journal	November 2008
New Sensitizer-Modified Calix[4]arenes Enabling Near-UV Excitation of Complexed Luminescent Lanthanide Ions Steemers, Frank J.; Verboom, Willem; Reinhoudt, David N. Journal of the American Chemical Society, Vol. 117, Issue 37 https://doi.org/10.1021/ja00142a004	journal	September 1995
Multifunctionality and Crystal Dynamics of a Highly Stable, Porous Metal−Organic Framework [Zn ₄ O(NTB) ₂ ] Lee, Eun Young; Jang, Seung Yeon; Suh, Myunghyun Paik Journal of the American Chemical Society, Vol. 127, Issue 17 https://doi.org/10.1021/ja043756x	journal	May 2005
Self-Assembly of Heterobimetallic d−f Hybrid Complexes: Sensitization of Lanthanide Luminescence by d-Block Metal-to-Ligand Charge-Transfer Excited States Pope, Simon J. A.; Coe, Benjamin J.; Faulkner, Stephen Journal of the American Chemical Society, Vol. 126, Issue 31 https://doi.org/10.1021/ja047523h	journal	August 2004
Turn-On Fluorescence in Tetraphenylethylene-Based Metal–Organic Frameworks: An Alternative to Aggregation-Induced Emission Shustova, Natalia B.; McCarthy, Brian D.; Dincă, Mircea Journal of the American Chemical Society, Vol. 133, Issue 50 https://doi.org/10.1021/ja209327q	journal	December 2011
Conformational Locking by Design: Relating Strain Energy with Luminescence and Stability in Rigid Metal–Organic Frameworks Shustova, Natalia B.; Cozzolino, Anthony F.; Dincă, Mircea Journal of the American Chemical Society, Vol. 134, Issue 48 https://doi.org/10.1021/ja3103154	journal	November 2012
Tunable Rare-Earth fcu-MOFs: A Platform for Systematic Enhancement of CO₂ Adsorption Energetics and Uptake Xue, Dong-Xu; Cairns, Amy J.; Belmabkhout, Youssef Journal of the American Chemical Society, Vol. 135, Issue 20, p. 7660-7667 https://doi.org/10.1021/ja401429x	journal	May 2013
Rigidifying Fluorescent Linkers by Metal–Organic Framework Formation for Fluorescence Blue Shift and Quantum Yield Enhancement Wei, Zhangwen; Gu, Zhi-Yuan; Arvapally, Ravi K. Journal of the American Chemical Society, Vol. 136, Issue 23 https://doi.org/10.1021/ja5006866	journal	May 2014
A Guest-Responsive Fluorescent 3D Microporous Metal−Organic Framework Derived from a Long-Lifetime Pyrene Core Stylianou, Kyriakos C.; Heck, Romain; Chong, Samantha Y. Journal of the American Chemical Society, Vol. 132, Issue 12, p. 4119-4130 https://doi.org/10.1021/ja906041f	journal	March 2010
Near-Infrared Luminescent Lanthanide MOF Barcodes White, Kiley A.; Chengelis, Demetra A.; Gogick, Kristy A. Journal of the American Chemical Society, Vol. 131, Issue 50 https://doi.org/10.1021/ja907885m	journal	December 2009
Luminescent Oxygen-Sensitive Ink to Produce Highly Secured Anticounterfeiting Labels by Inkjet Printing Ding, Longjiang; Wang, Xu-dong Journal of the American Chemical Society, Vol. 142, Issue 31 https://doi.org/10.1021/jacs.0c05506	journal	July 2020
Linker Desymmetrization: Access to a Series of Rare-Earth Tetracarboxylate Frameworks with Eight-Connected Hexanuclear Nodes Lv, Xiu-Liang; Feng, Liang; Xie, Lin-Hua Journal of the American Chemical Society, Vol. 143, Issue 7 https://doi.org/10.1021/jacs.0c11546	journal	January 2021
Fluoro-Bridged Clusters in Rare-Earth Metal–Organic Frameworks Vizuet, Juan P.; Mortensen, Marie L.; Lewis, Abigail L. Journal of the American Chemical Society, Vol. 143, Issue 43 https://doi.org/10.1021/jacs.1c10493	journal	October 2021
A Fine-Tuned Metal–Organic Framework for Autonomous Indoor Moisture Control AbdulHalim, Rasha G.; Bhatt, Prashant M.; Belmabkhout, Youssef Journal of the American Chemical Society, Vol. 139, Issue 31 https://doi.org/10.1021/jacs.7b04132	journal	July 2017
Discovery and introduction of a (3,18)-connected net as an ideal blueprint for the design of metal–organic frameworks Guillerm, Vincent; Weseliński, Łukasz J.; Belmabkhout, Youssef Nature Chemistry, Vol. 6, Issue 8 https://doi.org/10.1038/nchem.1982	journal	June 2014
Geminate labels programmed by two-tone microdroplets combining structural and fluorescent color Qin, Lang; Liu, Xiaojun; He, Kunyun Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-20908-y	journal	January 2021
Luminescent multifunctional lanthanides-based metal–organic frameworks Rocha, João; Carlos, Luís D.; Paz, Filipe A. Almeida Chem. Soc. Rev., Vol. 40, Issue 2 https://doi.org/10.1039/C0CS00130A	journal	January 2011
Efficient synthesis of pyrene-1-carbothioamides and carboxamides. Tunable solid-state fluorescence of pyrene-1-carboxamides Wrona-Piotrowicz, Anna; Zakrzewski, Janusz; Métivier, Rémi RSC Adv., Vol. 4, Issue 99 https://doi.org/10.1039/C4RA07045C	journal	January 2014
Versatile rare earth hexanuclear clusters for the design and synthesis of highly-connected ftw -MOFs Luebke, Ryan; Belmabkhout, Youssef; Weseliński, Łukasz J. Chemical Science, Vol. 6, Issue 7 https://doi.org/10.1039/C5SC00614G	journal	January 2015
Biocompatible MOFs with high absolute quantum yield for bioimaging in the second near infrared window Sava Gallis, Dorina F.; Butler, Kimberly S.; Rohwer, Lauren E. S. CrystEngComm, Vol. 20, Issue 39 https://doi.org/10.1039/C8CE00909K	journal	January 2018
Blue, green, and red full-color ultralong afterglow in nitrogen-doped carbon dots Lin, Cunjian; Zhuang, Yixi; Li, Wuhui Nanoscale, Vol. 11, Issue 14 https://doi.org/10.1039/C8NR09672D	journal	January 2019
Lanthanide-based molecular alloys with hydroxyterephthalate: a versatile system Wang, Jinzeng; Suffren, Yan; Daiguebonne, Carole CrystEngComm, Vol. 23, Issue 1 https://doi.org/10.1039/D0CE00947D	journal	January 2021
Luminescent metal–organic frameworks Allendorf, M. D.; Bauer, C. A.; Bhakta, R. K. Chemical Society Reviews, Vol. 38, Issue 5 https://doi.org/10.1039/b802352m	journal	January 2009
Multicolor upconverted luminescence-encoded superparticles via controlling self-assembly based on hydrophobic lanthanide-doped NaYF4 nanocrystals Zhang, Qingbin; Wang, Xin; Zhu, Yimin Journal of Materials Chemistry, Vol. 21, Issue 32 https://doi.org/10.1039/c1jm10350d	journal	January 2011

Similar Records

Programmable Photoluminescence via Intrinsic and DNA-Fluorophore Association in a Mixed Cluster Heterometallic MOF

Journal Article · Tue Feb 15 19:00:00 EST 2022 · ACS Applied Materials and Interfaces · OSTI ID:1855803

Optical tags comprising rare earth metal-organic frameworks

Patent · Tue Sep 26 00:00:00 EDT 2023 · OSTI ID:2222361

Orthogonal luminescence lifetime encoding by intermetallic energy transfer in heterometallic rare-earth MOFs

Journal Article · Tue Feb 21 19:00:00 EST 2023 · Nature Communications · OSTI ID:2311613

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
covert tag
energy transfer
metal-organic frameworks
optical tag
rare earth

CCDC 2266109: Experimental Crystal Structure Determination I., Deneff, Jacob; S., Rohwer, Lauren E.; S., Butler, Kimberly https://doi.org/10.5517/ccdc.csd.cc2g229y The current record is supplemented by this dataset	dataset	January 2023
CCDC 2266110: Experimental Crystal Structure Determination I., Deneff, Jacob; S., Rohwer, Lauren E.; S., Butler, Kimberly https://doi.org/10.5517/ccdc.csd.cc2g22bz The current record is supplemented by this dataset	dataset	January 2023
CCDC 2266111: Experimental Crystal Structure Determination I., Deneff, Jacob; S., Rohwer, Lauren E.; S., Butler, Kimberly https://doi.org/10.5517/ccdc.csd.cc2g22c0 The current record is supplemented by this dataset	dataset	January 2023
CCDC 2266112: Experimental Crystal Structure Determination I., Deneff, Jacob; S., Rohwer, Lauren E.; S., Butler, Kimberly https://doi.org/10.5517/ccdc.csd.cc2g22d1 The current record is supplemented by this dataset	dataset	January 2023

Covert MOF-Based Photoluminescent Tags via Tunable Linker Energetics

Citation Formats

References (49)

Linked Research (4)

Similar Records

Related Subjects