Engineering the Optical Response of the Titanium-MIL-125 Metal–Organic Framework through Ligand Functionalization,Journal of the American Chemical Society

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Engineering the Optical Response of the Titanium-MIL-125 Metal–Organic Framework through Ligand Functionalization
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2013-07-15 , DOI: 10.1021/ja405350u
Christopher H. Hendon ₁ , Davide Tiana ₁ , Marc Fontecave ₂ , Clément Sanchez ₃ , Loïc D’arras ₃ , Capucine Sassoye ₃ , Laurence Rozes ₃ , Caroline Mellot-Draznieks ₂ , Aron Walsh ₁

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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.

中文翻译：

通过配体功能化设计钛-MIL-125 金属-有机框架的光学响应

在此，我们讨论了 MIL-125（一种 TiO2/1,4-苯二羧酸盐 (bdc) 金属有机骨架 (MOF)）的带隙改性。通过合成和计算的结合，我们阐明了带有胺化接头的 MIL-125 的电子结构。当使用单胺化 bdc-NH2 接头时观察到的带隙减小是由于将 N 2p 电子捐赠给芳族连接单元，导致带红移高于 MIL-125 的价带边缘。我们进一步探索了在硅 MIL-125 中使用二胺化接头 bdc-(NH2)2 和其他官能团 (-OH、-CH3、-Cl) 作为替代替代来控制光学响应。预计 bdc-(NH2)2 连接单元会将 MIL-125 的带隙降低至 1.28 eV，这通过基于 bdc-(NH2)2 的 MIL-125 的靶向合成得到证实。

更新日期：2013-07-15

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