Alkaline Earth Metal Ion/Dihydroxy-Terephthalate MOFs: Structural Diversity and Unusual Luminescent Properties

Antigoni Douvali, Giannis S. Papaefstathiou, Maria Pia Gullo, Andrea Barbieri, Athanassios C. Tsipis, Christos D. Malliakas, Mercouri G Kanatzidis, Ioannis Papadas, Gerasimos S. Armatas, Antonios G. Hatzidimitriou, Theodore Lazarides, Manolis J. Manos

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

Alkaline earth (group 2) metal ion organic frameworks (AEMOFs) represent an important subcategory of MOFs with interesting structures and physical properties. Five MOFs, namely, [Mg2(H2dhtp)2(μ-H2O)(NMP)4] (AEMOF-2), [Mg2(H2dhtp)1.5(DMAc)4]Cl·DMAc (AEMOF-3), [Ca(H2dhtp)(DMAc)2] (AEMOF-4), [Sr3(H2dhtp)3(DMAc)6]·H2O (AEMOF-5), and [Ba(H2dhtp)(DMAc)] (AEMOF-6) (H4dhtp = 2,5-dihydroxy-terepthalic acid; DMAc = N,N-dimethylacetamide; NMP = N-methylpyrrolidone), are presented herein. The reported MOFs display structural variety with diverse topologies and new structural features. Interestingly, AEMOF-6 is the first example of a Ba2+-H2dhtp2- MOF, and AEMOF-5 is only the second known Sr2+-H2dhtp2- MOF. Detailed photoluminescence studies revealed alkaline earth metal ion-dependent fluorescence properties of the materials, with the heavier alkaline earth metal ions exhibiting red-shifted emission with respect to the lighter ions at room temperature. A bathochromic shift of the emission was observed for the MOFs (mostly for AEMOF-3 and AEMOF-4) at 77 K as a result of excited state proton transfer (ESIPT), which involves an intramolecular proton transfer from a hydroxyl to an adjacent carboxylic group of the H2dhtp2- ligand. Remarkably, AEMOF-6 displays rare yellow fluorescence at room temperature, which is attractive for solid state lighting applications. To probe whether the alkaline earth metal ions are responsible for the unusual luminescence properties of the reported MOFs, the potential energy surfaces (PESs) of the ground, S0, and lowest energy excited singlet, S1, states of model complexes along the intramolecular proton transfer coordinate were calculated by DFT and TD-DFT methods.

Original languageEnglish
Pages (from-to)5813-5826
Number of pages14
JournalInorganic Chemistry
Volume54
Issue number12
DOIs
Publication statusPublished - Jun 15 2015

Fingerprint

Alkaline Earth Metals
terephthalate
alkaline earth metals
Proton transfer
Metal ions
metal ions
Discrete Fourier transforms
protons
Fluorescence
fluorescence
Potential energy surfaces
room temperature
heavy metals
Excited states
Hydroxyl Radical
illuminating
Heavy metals
Luminescence
Photoluminescence
topology

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Douvali, A., Papaefstathiou, G. S., Gullo, M. P., Barbieri, A., Tsipis, A. C., Malliakas, C. D., ... Manos, M. J. (2015). Alkaline Earth Metal Ion/Dihydroxy-Terephthalate MOFs: Structural Diversity and Unusual Luminescent Properties. Inorganic Chemistry, 54(12), 5813-5826. https://doi.org/10.1021/acs.inorgchem.5b00539

Alkaline Earth Metal Ion/Dihydroxy-Terephthalate MOFs : Structural Diversity and Unusual Luminescent Properties. / Douvali, Antigoni; Papaefstathiou, Giannis S.; Gullo, Maria Pia; Barbieri, Andrea; Tsipis, Athanassios C.; Malliakas, Christos D.; Kanatzidis, Mercouri G; Papadas, Ioannis; Armatas, Gerasimos S.; Hatzidimitriou, Antonios G.; Lazarides, Theodore; Manos, Manolis J.

In: Inorganic Chemistry, Vol. 54, No. 12, 15.06.2015, p. 5813-5826.

Research output: Contribution to journalArticle

Douvali, A, Papaefstathiou, GS, Gullo, MP, Barbieri, A, Tsipis, AC, Malliakas, CD, Kanatzidis, MG, Papadas, I, Armatas, GS, Hatzidimitriou, AG, Lazarides, T & Manos, MJ 2015, 'Alkaline Earth Metal Ion/Dihydroxy-Terephthalate MOFs: Structural Diversity and Unusual Luminescent Properties', Inorganic Chemistry, vol. 54, no. 12, pp. 5813-5826. https://doi.org/10.1021/acs.inorgchem.5b00539
Douvali A, Papaefstathiou GS, Gullo MP, Barbieri A, Tsipis AC, Malliakas CD et al. Alkaline Earth Metal Ion/Dihydroxy-Terephthalate MOFs: Structural Diversity and Unusual Luminescent Properties. Inorganic Chemistry. 2015 Jun 15;54(12):5813-5826. https://doi.org/10.1021/acs.inorgchem.5b00539
Douvali, Antigoni ; Papaefstathiou, Giannis S. ; Gullo, Maria Pia ; Barbieri, Andrea ; Tsipis, Athanassios C. ; Malliakas, Christos D. ; Kanatzidis, Mercouri G ; Papadas, Ioannis ; Armatas, Gerasimos S. ; Hatzidimitriou, Antonios G. ; Lazarides, Theodore ; Manos, Manolis J. / Alkaline Earth Metal Ion/Dihydroxy-Terephthalate MOFs : Structural Diversity and Unusual Luminescent Properties. In: Inorganic Chemistry. 2015 ; Vol. 54, No. 12. pp. 5813-5826.
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AU - Papaefstathiou, Giannis S.

AU - Gullo, Maria Pia

AU - Barbieri, Andrea

AU - Tsipis, Athanassios C.

AU - Malliakas, Christos D.

AU - Kanatzidis, Mercouri G

AU - Papadas, Ioannis

AU - Armatas, Gerasimos S.

AU - Hatzidimitriou, Antonios G.

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N2 - Alkaline earth (group 2) metal ion organic frameworks (AEMOFs) represent an important subcategory of MOFs with interesting structures and physical properties. Five MOFs, namely, [Mg2(H2dhtp)2(μ-H2O)(NMP)4] (AEMOF-2), [Mg2(H2dhtp)1.5(DMAc)4]Cl·DMAc (AEMOF-3), [Ca(H2dhtp)(DMAc)2] (AEMOF-4), [Sr3(H2dhtp)3(DMAc)6]·H2O (AEMOF-5), and [Ba(H2dhtp)(DMAc)] (AEMOF-6) (H4dhtp = 2,5-dihydroxy-terepthalic acid; DMAc = N,N-dimethylacetamide; NMP = N-methylpyrrolidone), are presented herein. The reported MOFs display structural variety with diverse topologies and new structural features. Interestingly, AEMOF-6 is the first example of a Ba2+-H2dhtp2- MOF, and AEMOF-5 is only the second known Sr2+-H2dhtp2- MOF. Detailed photoluminescence studies revealed alkaline earth metal ion-dependent fluorescence properties of the materials, with the heavier alkaline earth metal ions exhibiting red-shifted emission with respect to the lighter ions at room temperature. A bathochromic shift of the emission was observed for the MOFs (mostly for AEMOF-3 and AEMOF-4) at 77 K as a result of excited state proton transfer (ESIPT), which involves an intramolecular proton transfer from a hydroxyl to an adjacent carboxylic group of the H2dhtp2- ligand. Remarkably, AEMOF-6 displays rare yellow fluorescence at room temperature, which is attractive for solid state lighting applications. To probe whether the alkaline earth metal ions are responsible for the unusual luminescence properties of the reported MOFs, the potential energy surfaces (PESs) of the ground, S0, and lowest energy excited singlet, S1, states of model complexes along the intramolecular proton transfer coordinate were calculated by DFT and TD-DFT methods.

AB - Alkaline earth (group 2) metal ion organic frameworks (AEMOFs) represent an important subcategory of MOFs with interesting structures and physical properties. Five MOFs, namely, [Mg2(H2dhtp)2(μ-H2O)(NMP)4] (AEMOF-2), [Mg2(H2dhtp)1.5(DMAc)4]Cl·DMAc (AEMOF-3), [Ca(H2dhtp)(DMAc)2] (AEMOF-4), [Sr3(H2dhtp)3(DMAc)6]·H2O (AEMOF-5), and [Ba(H2dhtp)(DMAc)] (AEMOF-6) (H4dhtp = 2,5-dihydroxy-terepthalic acid; DMAc = N,N-dimethylacetamide; NMP = N-methylpyrrolidone), are presented herein. The reported MOFs display structural variety with diverse topologies and new structural features. Interestingly, AEMOF-6 is the first example of a Ba2+-H2dhtp2- MOF, and AEMOF-5 is only the second known Sr2+-H2dhtp2- MOF. Detailed photoluminescence studies revealed alkaline earth metal ion-dependent fluorescence properties of the materials, with the heavier alkaline earth metal ions exhibiting red-shifted emission with respect to the lighter ions at room temperature. A bathochromic shift of the emission was observed for the MOFs (mostly for AEMOF-3 and AEMOF-4) at 77 K as a result of excited state proton transfer (ESIPT), which involves an intramolecular proton transfer from a hydroxyl to an adjacent carboxylic group of the H2dhtp2- ligand. Remarkably, AEMOF-6 displays rare yellow fluorescence at room temperature, which is attractive for solid state lighting applications. To probe whether the alkaline earth metal ions are responsible for the unusual luminescence properties of the reported MOFs, the potential energy surfaces (PESs) of the ground, S0, and lowest energy excited singlet, S1, states of model complexes along the intramolecular proton transfer coordinate were calculated by DFT and TD-DFT methods.

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