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

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Hendon, Christopher H.
Tiana, Davide
Fontecave, Marc
Sanchez, Clement
D'arras, Loic
Sassoye, Capucine
Rozes, Laurence
Mellot-Draznieks, Caroline
Walsh, Aron
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American Chemical Society (ACS)
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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.
CO2 capture , Band-gaps , MOFS , Photocatalyst , Substitution , Tunability , Separation , Reduction , Catalysis , Amino
Hendon, C. H., Tiana, D., Fontecave, M., Sanchez, C., D’arras, L., Sassoye, C., Rozes, L., Mellot-Draznieks, C. and 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), pp. 10942-10945. doi: 10.1021/ja405350u
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