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

Christopher H. Hendon, Davide Tiana, Marc Fontecave, Clément Sanchez, Loïc D'Arras, Capucine Sassoye, Laurence Rozes, Caroline Mellot-Draznieks, Aron Walsh

Research output: Contribution to journalArticlepeer-review

680 Scopus citations


Herein we discuss band gap modification of MIL-125, a TiO 2/1,4-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.

Original languageEnglish
Pages (from-to)10942-10945
Number of pages4
JournalJournal of the American Chemical Society
Issue number30
StatePublished - 31 Jul 2013


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