TY - JOUR

T1 - Highly Luminescent Lanthanide Metal-Organic Frameworks with Tunable Color for Nanomolar Detection of Iron(III), Ofloxacin and Gossypol and Anti-counterfeiting Applications

AU - Yu, Xiaolin

AU - Ryadun, Alexey A

AU - Pavlov, Dmitry I

AU - Guselnikova, Tatiana Y

AU - Potapov, Andrei S

AU - Fedin, Vladimir P

N1 - This work was supported by the Russian Science Foundation, grant No. 23-43-00017. NIIC analytical characterization facilities used in this work operate with support from the Ministry of Science and Higher Education of the Russian Federation, project numbers 121031700321-3 and 121031700313-8. Xiaolin Yugratefully appreciates the financial support of China Scholarship Council (CSC, grant No. 202008090088) for his postgraduate course at Novosibirsk State University. The Siberian Branch of the Russian Academy of Sciences (SB RAS) Siberian Supercomputer Center is gratefully acknowledged for providing supercomputer facilities. © 2023 Wiley-VCH GmbH.

PY - 2023/8/28

Y1 - 2023/8/28

N2 - Solvothermal reaction of 5,5'-(pyridine-2,6-diylbis(oxy))diisophthalic acid (H4L) with europium(III) or terbium(III) nitrates in acetonitrile-water (1:1) at 120 °C gave rise to isostructural 2D coordination polymers, [Ln(HL)(H2O)3]∞ (NIIC-1-Eu and NIIC-1-Tb), the layers of which are composed by eight-coordinated lanthanide(III) ions interconnected by triply deprotonated ligands HL3-. The layers are packed in the crystal without any specific intermolecular interactions between them, allowing the facile preparation of stable water suspensions, in which NIIC-1-Tb exhibited top-performing sensing properties through luminescence quenching effect with exceptionally low detection limits towards Fe3+ (LOD 8.62 nM), ofloxacin (OFX) antibiotic (LOD 3.91 nM) and cotton phytotoxicant gossypol (LOD 2.27 nM). In addition to low detection limit and high selectivity, NIIC-1-Tb features fast sensing response (within 60-90 seconds), making it superior to other MOF-based sensors for metal cations and organic toxicants. The photoluminescence quantum yield of NIIC-1-Tb was 93%, one of the highest among lanthanide MOFs. Mixed-metal coordination polymers NIIC-1-EuxTb1-x demonstrated efficient photoluminescence, the color of which could be modulated by the excitation wavelength and time delay for emission monitoring (within 1 millisecond). Furthermore, an original 2D QR-coding scheme was designed for anti-counterfeiting labeling of goods based on unique and tunable emission spectra of NIIC-1-Ln coordination polymers.

AB - Solvothermal reaction of 5,5'-(pyridine-2,6-diylbis(oxy))diisophthalic acid (H4L) with europium(III) or terbium(III) nitrates in acetonitrile-water (1:1) at 120 °C gave rise to isostructural 2D coordination polymers, [Ln(HL)(H2O)3]∞ (NIIC-1-Eu and NIIC-1-Tb), the layers of which are composed by eight-coordinated lanthanide(III) ions interconnected by triply deprotonated ligands HL3-. The layers are packed in the crystal without any specific intermolecular interactions between them, allowing the facile preparation of stable water suspensions, in which NIIC-1-Tb exhibited top-performing sensing properties through luminescence quenching effect with exceptionally low detection limits towards Fe3+ (LOD 8.62 nM), ofloxacin (OFX) antibiotic (LOD 3.91 nM) and cotton phytotoxicant gossypol (LOD 2.27 nM). In addition to low detection limit and high selectivity, NIIC-1-Tb features fast sensing response (within 60-90 seconds), making it superior to other MOF-based sensors for metal cations and organic toxicants. The photoluminescence quantum yield of NIIC-1-Tb was 93%, one of the highest among lanthanide MOFs. Mixed-metal coordination polymers NIIC-1-EuxTb1-x demonstrated efficient photoluminescence, the color of which could be modulated by the excitation wavelength and time delay for emission monitoring (within 1 millisecond). Furthermore, an original 2D QR-coding scheme was designed for anti-counterfeiting labeling of goods based on unique and tunable emission spectra of NIIC-1-Ln coordination polymers.

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85165254897&origin=inward&txGid=3029821864a4f13b9244ed50972d5501

U2 - 10.1002/anie.202306680

DO - 10.1002/anie.202306680

M3 - Article

C2 - 37414736

VL - 62

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

SN - 1433-7851

IS - 35

M1 - e202306680

ER -