Engineering the optical response of the titanium-MIL-125 metal-organic framework through ligand functionalization

C.H. Hendon, D. Tiana, M. Fontecave, C. Sanchez, L. D'Arras, C. Sassoye, L. Rozes, C. Mellot-Draznieks, A. Walsh

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Abstract

Herein we discuss band gap modification of MIL-125, a TiO2/1,4-benzenedicarboxylate (bdc) metal–organic framework (MOF). Through a combination of synthesis and computation, we elucidated the electronic structure of MIL-125 with aminated linkers. The band gap decrease observed when the monoaminated bdc-NH2 linker was used arises from donation of the N 2p electrons to the aromatic linking unit, resulting in a red-shifted band above the valence-band edge of MIL-125. We further explored in silico MIL-125 with the diaminated linker bdc-(NH2)2 and other functional groups (−OH, −CH3, −Cl) as alternative substitutions to control the optical response. The bdc-(NH2)2 linking unit was predicted to lower the band gap of MIL-125 to 1.28 eV, and this was confirmed through the targeted synthesis of the bdc-(NH2)2-based MIL-125. This study illustrates the possibility of tuning the optical response of MOFs through rational functionalization of the linking unit, and the strength of combined synthetic/computational approaches for targeting functionalized hybrid materials.
LanguageEnglish
Pages10942-10945
Number of pages4
JournalJournal of the American Chemical Society
Volume135
Issue number30
Early online date10 Jul 2013
DOIs
StatusPublished - 31 Jul 2013

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Titanium
Energy gap
Metals
Ligands
Hybrid materials
Valence bands
Functional groups
Electronic structure
Substitution reactions
Tuning
Electrons
Computer Simulation
N(1)-methyl-2-lysergic acid diethylamide

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Hendon, C. H., Tiana, D., Fontecave, M., Sanchez, C., D'Arras, L., Sassoye, C., ... Walsh, A. (2013). Engineering the optical response of the titanium-MIL-125 metal-organic framework through ligand functionalization. Journal of the American Chemical Society, 135(30), 10942-10945. https://doi.org/10.1021/ja405350u

Engineering the optical response of the titanium-MIL-125 metal-organic framework through ligand functionalization. / Hendon, C.H.; Tiana, D.; Fontecave, M.; Sanchez, C.; D'Arras, L.; Sassoye, C.; Rozes, L.; Mellot-Draznieks, C.; Walsh, A.

In: Journal of the American Chemical Society, Vol. 135, No. 30, 31.07.2013, p. 10942-10945.

Research output: Contribution to journalArticle

Hendon, CH, Tiana, D, Fontecave, M, Sanchez, C, D'Arras, L, Sassoye, C, Rozes, L, Mellot-Draznieks, C & Walsh, A 2013, 'Engineering the optical response of the titanium-MIL-125 metal-organic framework through ligand functionalization' Journal of the American Chemical Society, vol. 135, no. 30, pp. 10942-10945. https://doi.org/10.1021/ja405350u
Hendon, C.H. ; Tiana, D. ; Fontecave, M. ; Sanchez, C. ; D'Arras, L. ; Sassoye, C. ; Rozes, L. ; Mellot-Draznieks, C. ; Walsh, A. / Engineering the optical response of the titanium-MIL-125 metal-organic framework through ligand functionalization. In: Journal of the American Chemical Society. 2013 ; Vol. 135, No. 30. pp. 10942-10945.
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