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

doi:10.1021/acs.inorgchem.5b00539

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

^*Corresponding author for this work

Chemistry

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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⁺-H₂dhtp^2- MOF, and AEMOF-5 is only the second known Sr²⁺-H₂dhtp^2- 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 H₂dhtp^2- 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 language	English (US)
Pages (from-to)	5813-5826
Number of pages	14
Journal	Inorganic chemistry
Volume	54
Issue number	12
DOIs	https://doi.org/10.1021/acs.inorgchem.5b00539
State	Published - Jun 15 2015

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/acs.inorgchem.5b00539

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Douvali, A., Papaefstathiou, G. S., Gullo, M. P., Barbieri, A., Tsipis, A. C., Malliakas, C. D., Kanatzidis, M. G., Papadas, I., Armatas, G. S., Hatzidimitriou, A. G., Lazarides, T., & 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

@article{2f130a4a43e94cc39c14dead58d1f62d,

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

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.",

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

note = "Publisher Copyright: {\textcopyright} 2015 American Chemical Society.",

year = "2015",

month = jun,

day = "15",

doi = "10.1021/acs.inorgchem.5b00539",

language = "English (US)",

volume = "54",

pages = "5813--5826",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "12",

}

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

TY - JOUR

T1 - Alkaline Earth Metal Ion/Dihydroxy-Terephthalate MOFs

T2 - Structural Diversity and Unusual Luminescent Properties

AU - Douvali, Antigoni

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.

AU - Lazarides, Theodore

AU - Manos, Manolis J.

PY - 2015/6/15

Y1 - 2015/6/15

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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DO - 10.1021/acs.inorgchem.5b00539

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JO - Inorganic chemistry

JF - Inorganic chemistry

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ER -

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

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

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CCDC 1042419: Experimental Crystal Structure Determination

CCDC 1042420: Experimental Crystal Structure Determination

CCDC 1042418: Experimental Crystal Structure Determination

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