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

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 b...

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Vydáno v:Journal of the American Chemical Society Ročník 135; číslo 30; s. 10942 - 10945
Hlavní autoři: Hendon, Christopher H, Tiana, Davide, Fontecave, Marc, Sanchez, Clément, D’arras, Loïc, Sassoye, Capucine, Rozes, Laurence, Mellot-Draznieks, Caroline, Walsh, Aron
Médium: Journal Article
Jazyk:angličtina
Vydáno: United States American Chemical Society 31.07.2013
Témata:
Engineering
Ligands
Models, Molecular
Molecular Conformation
Optical Phenomena
Organometallic Compounds - chemistry
Phthalic Acids - chemistry
Titanium - chemistry
ISSN:0002-7863, 1520-5126, 1520-5126
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Shrnutí: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-NH 2 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-(NH 2 ) 2 and other functional groups (−OH, −CH3, −Cl) as alternative substitutions to control the optical response. The bdc-(NH 2 ) 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-(NH 2 ) 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.
Bibliografie:ObjectType-Article-1
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ISSN:0002-7863
1520-5126
1520-5126
DOI:10.1021/ja405350u