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Tuned Hydrogen Bonding in Rare-Earth Metal–Organic Frameworks for Design of Optical and Electronic Properties: An Exemplar Study of Y–2,5-Dihydroxyterephthalic Acid
journal contribution
posted on 2020-01-14, 23:14 authored by Dayton
J. Vogel, Tina M. Nenoff, Jessica M. RimszaOrganic linkers in
metal–organic framework (MOF) materials
exhibit differences in hydrogen bonding (H-bonding), which can alter
the geometric, electronic, and optical properties of the MOF. Density
functional theory (DFT) simulations were performed on a photoluminescent
Y-2,5-dihydroxyterephthalic acid (DOBDC) MOF with H-bonding concentrations
between 0 and 100%; the H-bonds were located on both bidentate- and
monodentate-bound DOBDC linkers. At 0% H-bond concentration in the
framework, the lattice parameters contracted, the density increased,
and simulated X-ray diffraction patterns shifted. Comparison with
published experimental data identified that Y–DOBDC MOF structures
must have a degree of H-bond concentration. The concentration of H-bonds
in the system shifted the calculated band gap energy from 2.25 eV
at 100% to 3.00 eV at 0%. The band gap energies also indicate a distinction
of H-bonds formed on bidentate-coordinated linkers compared to those
on monodentate linkers. Additionally, when the calculated optical
spectra are compared with experimental data, the ligand-to-ligand
charge-transfer luminescence in Y–DOBDC MOFs is expected to
result from an average of 20–40% H-bonding with at least 50%
of the bidentate linkers containing H-bonding. Therefore, the type
of H-bonding within the DOBDC linker determines the electronic structure
and the optical absorption of the MOF framework structure. Tuning
of the H-bonding in rare-earth MOFs provides an opportunity to control
the specific optical and adsorption properties of the MOF framework
on the basis of reactions between the linker and the environment.
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Keywords
band gap energiesH-bonding concentrationsTuned Hydrogen Bondingrare-earth MOFsMOF frameworkExemplar Studyadsorption propertiesOrganic linkersbidentate linkersbidentate-coordinated linkersH-bond concentrationmaterials exhibit differencesmonodentate-bound DOBDC linkersligand-to-ligand charge-transfer luminescenceDFTElectronic Propertiesmonodentate linkers2.25 eVDOBDC linkerMOF framework structureX-ray diffraction patternsband gap energylattice parameters3.00 eV
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