Engineering the Optical Response of the Titanium-MIL-125 Metal鈥揙rganic Framework through Ligand Functionalization

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• 作者：Christopher H. Hendon ; Davide Tiana ; Marc Fontecave ; Cl茅ment Sanchez ; Lo茂c D鈥檃rras ; Capucine Sassoye ; Laurence Rozes ; Caroline Mellot-Draznieks ; Aron Walsh
• 刊名：The Journal of the American Chemical Society
• 出版年：2013
• 出版时间：July 31, 2013
• 年：2013
• 卷：135
• 期：30
• 页码：10942-10945
• 全文大小：330K
• 年卷期：v.135,no.30(July 31, 2013)
• ISSN：1520-5126

文摘

Herein we discuss band gap modification of MIL-125, a TiO₂/1,4-benzenedicarboxylate (bdc) metal鈥搊rganic 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 (鈭扥H, 鈭扖H₃, 鈭扖l) 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.