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Title: Anthracene-Based Lanthanide Metal-Organic Frameworks: Synthesis, Structure, Photoluminescence, and Radioluminescence Properties

Abstract

Four anthracene-based lanthanide metal-organic framework structures (MOFs) were synthesized from the combination of the lanthanide ions, Eu 3+, Tb 3+, Er 3+, and Tm 3+, with 9,10-anthracenedicarboxylic acid (H 2ADC) in dimethylformamide (DMF) under hydrothermal conditions. The 3-D networks crystalize in the triclinic system with P-1 space group with the following compositions: (i) {{[Ln 2(ADC) 3(DMF) 4·DMF]} n, Ln = Eu (1) and Tb (2)} and (ii) {{[Ln 2(ADC) 3(DMF) 2(OH 2) 2·2DMF·H 2O]} n, Ln = Er (3) and Tm (4)}. The metal centers exist in various coordination environments; nine coordinate in (i), while seven and eight coordinate in (ii). The deprotonated ligand, ADC, assumes multiple coordination modes, with its carboxylate functional groups severely twisted away from the plane of the anthracene moiety. The structures show ligand-based photoluminescence, which appears to be significantly quenched when compared with that of the parent H 2ADC solid powder. Structure 2 is the least quenched and showed an average photoluminescence lifetime from bi-exponential decay of 0.3 ns. On exposure to ionizing radiation, the structures show radioluminescence spectral features that are consistent with the isolation of the ligand units in its 3-D network. The spectral features vary among the 3-D networks and appear tomore » suggest that the latter undergo significant changes in their molecular and/or electronic structure in the presence of the ionizing radiation.« less

Authors:
; ; ;
Publication Date:
Research Org.:
Clark Atlanta Univ., Atlanta, GA (United States); Univ. of California, Riverside, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1422449
Alternate Identifier(s):
OSTI ID: 1507356
Grant/Contract Number:  
NA0000979; FE0022952
Resource Type:
Published Article
Journal Name:
Crystals
Additional Journal Information:
Journal Name: Crystals Journal Volume: 8 Journal Issue: 1; Journal ID: ISSN 2073-4352
Publisher:
MDPI AG
Country of Publication:
Germany
Language:
English
Subject:
36 MATERIALS SCIENCE; lanthanide coordination polymers; crystal structures; metal-organic framework fluorescence; radioluminescence; lanthanide metal-organic framework; lanthanide anthracene dicarboxylate coordination polymers

Citation Formats

Mathis, II, Stephan, Golafale, Saki, Solntsev, Kyril, and Ingram, Conrad. Anthracene-Based Lanthanide Metal-Organic Frameworks: Synthesis, Structure, Photoluminescence, and Radioluminescence Properties. Germany: N. p., 2018. Web. doi:10.3390/cryst8010053.
Mathis, II, Stephan, Golafale, Saki, Solntsev, Kyril, & Ingram, Conrad. Anthracene-Based Lanthanide Metal-Organic Frameworks: Synthesis, Structure, Photoluminescence, and Radioluminescence Properties. Germany. doi:10.3390/cryst8010053.
Mathis, II, Stephan, Golafale, Saki, Solntsev, Kyril, and Ingram, Conrad. Mon . "Anthracene-Based Lanthanide Metal-Organic Frameworks: Synthesis, Structure, Photoluminescence, and Radioluminescence Properties". Germany. doi:10.3390/cryst8010053.
@article{osti_1422449,
title = {Anthracene-Based Lanthanide Metal-Organic Frameworks: Synthesis, Structure, Photoluminescence, and Radioluminescence Properties},
author = {Mathis, II, Stephan and Golafale, Saki and Solntsev, Kyril and Ingram, Conrad},
abstractNote = {Four anthracene-based lanthanide metal-organic framework structures (MOFs) were synthesized from the combination of the lanthanide ions, Eu3+, Tb3+, Er3+, and Tm3+, with 9,10-anthracenedicarboxylic acid (H2ADC) in dimethylformamide (DMF) under hydrothermal conditions. The 3-D networks crystalize in the triclinic system with P-1 space group with the following compositions: (i) {{[Ln2(ADC)3(DMF)4·DMF]}n, Ln = Eu (1) and Tb (2)} and (ii) {{[Ln2(ADC)3(DMF)2(OH2)2·2DMF·H2O]}n, Ln = Er (3) and Tm (4)}. The metal centers exist in various coordination environments; nine coordinate in (i), while seven and eight coordinate in (ii). The deprotonated ligand, ADC, assumes multiple coordination modes, with its carboxylate functional groups severely twisted away from the plane of the anthracene moiety. The structures show ligand-based photoluminescence, which appears to be significantly quenched when compared with that of the parent H2ADC solid powder. Structure 2 is the least quenched and showed an average photoluminescence lifetime from bi-exponential decay of 0.3 ns. On exposure to ionizing radiation, the structures show radioluminescence spectral features that are consistent with the isolation of the ligand units in its 3-D network. The spectral features vary among the 3-D networks and appear to suggest that the latter undergo significant changes in their molecular and/or electronic structure in the presence of the ionizing radiation.},
doi = {10.3390/cryst8010053},
journal = {Crystals},
number = 1,
volume = 8,
place = {Germany},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.3390/cryst8010053

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    Works referencing / citing this record:

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    • Advanced Materials, Vol. 21, Issue 1, p. 95-101
    • DOI: 10.1002/adma.200801753

    Regulation of π-Stacked Anthracene Arrangement for Fluorescence Modulation of Organic Solid from Monomer to Excited Oligomer Emission
    journal, February 2012

    • Hinoue, Tomoaki; Shigenoi, Yuta; Sugino, Misa
    • Chemistry - A European Journal, Vol. 18, Issue 15
    • DOI: 10.1002/chem.201103518

    Designing metal-organic frameworks for radiation detection
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    • Feng, Patrick L.; Branson, Janelle V.; Hattar, Khalid
    • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 652, Issue 1
    • DOI: 10.1016/j.nima.2011.01.102

    Synthesis, structures and adsorption properties of two new magnesium coordination polymers
    journal, February 2013


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    journal, September 2016


    Tuning the Formations of Metal–Organic Frameworks by Modification of Ratio of Reactant, Acidity of Reaction System, and Use of a Secondary Ligand
    journal, December 2011

    • Gao, Qian; Xie, Ya-Bo; Li, Jian-Rong
    • Crystal Growth & Design, Vol. 12, Issue 1
    • DOI: 10.1021/cg201059d

    Zn II Coordination Poylmers Based on 2,3,6,7-Anthracenetetracarboxylic Acid: Synthesis, Structures, and Luminescence Properties
    journal, November 2009

    • Chang, Ze; Zhang, Ai-Shun; Hu, Tong-Liang
    • Crystal Growth & Design, Vol. 9, Issue 11
    • DOI: 10.1021/cg900659r

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    journal, June 2011

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    • DOI: 10.1021/cr200101d

    Metal–Organic Framework Materials as Chemical Sensors
    journal, September 2011

    • Kreno, Lauren E.; Leong, Kirsty; Farha, Omar K.
    • Chemical Reviews, Vol. 112, Issue 2, p. 1105-1125
    • DOI: 10.1021/cr200324t

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    journal, October 2007

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    • DOI: 10.1021/ic701507r

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    • DOI: 10.1039/b802352m

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    • DOI: 10.1039/b906605e

    Cadmium(ii) coordination polymers based on a bulky anthracene-based dicarboxylate ligand: crystal structures and luminescent properties
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    • Liu, Chun-Sen; Wang, Jun-Jie; Chang, Ze
    • CrystEngComm, Vol. 12, Issue 6
    • DOI: 10.1039/b923516g

    Metal–organic frameworks as semiconductors
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    journal, April 2011


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    Metal–Organic Frameworks in Modern Physics: Highlights and Perspectives
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    • Mezenov, Yuri A.; Krasilin, Andrei A.; Dzyuba, Vladimir P.
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    Calcium-based efficient cathode-ray scintillating metal–organic frameworks constructed from π-conjugated luminescent motifs
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    • Lu, Jian; Wu, Hui-Fang; Wang, Wen-Fei
    • Chemical Communications, Vol. 55, Issue 92
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