TY - JOUR
T1 - Engineering the optical response of the titanium-MIL-125 metal-organic framework through ligand functionalization
AU - Hendon, Christopher H.
AU - Tiana, Davide
AU - Fontecave, Marc
AU - Sanchez, Clément
AU - D'Arras, Loïc
AU - Sassoye, Capucine
AU - Rozes, Laurence
AU - Mellot-Draznieks, Caroline
AU - Walsh, Aron
PY - 2013/7/31
Y1 - 2013/7/31
N2 - 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.
AB - 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.
UR - https://www.scopus.com/pages/publications/84881032415
U2 - 10.1021/ja405350u
DO - 10.1021/ja405350u
M3 - Article
AN - SCOPUS:84881032415
SN - 0002-7863
VL - 135
SP - 10942
EP - 10945
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 30
ER -