Статья

Engineering the Optical Response of the Titanium-MIL-125 Metal–Organic Framework through Ligand Functionalization

Christopher H. HendonDepartment of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.KDavide TianaDepartment of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.KMarc FontecaveLaboratoire de Chimie des Processus Biologiques, Collège de France, CNRS FRE 3488, 11 Place Marcelin Berthelot, 75005 Paris, FranceClément SánchezUPMC Univ Paris 06, UMR 7574, Chimie de la Matière Condensée de Paris, Collège de France, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, FranceLoïc D'ArrasUPMC Univ Paris 06, UMR 7574, Chimie de la Matière Condensée de Paris, Collège de France, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, FranceCapucine SassoyeUPMC Univ Paris 06, UMR 7574, Chimie de la Matière Condensée de Paris, Collège de France, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, FranceLaurence RozesUPMC Univ Paris 06, UMR 7574, Chimie de la Matière Condensée de Paris, Collège de France, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, FranceCaroline Mellot‐DraznieksLaboratoire de Chimie des Processus Biologiques, Collège de France, CNRS FRE 3488, 11 Place Marcelin Berthelot, 75005 Paris, FranceAron WalshDepartment of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K

2013en

ABI

Аннотация

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.

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Идентификаторы

DOI: 10.1021/ja405350u

Цитирования и источники

Цитирований: 2Использованных источников: 0

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