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通过配体功能化工程化钛-MIL-125 金属有机骨架的光学响应。

Engineering the optical response of the titanium-MIL-125 metal-organic framework through ligand functionalization.

机构信息

Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK.

出版信息

J Am Chem Soc. 2013 Jul 31;135(30):10942-5. doi: 10.1021/ja405350u. Epub 2013 Jul 15.

Abstract

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.

摘要

本文讨论了 MIL-125(一种 TiO2/1,4-苯二甲酸酯(bdc)金属有机骨架(MOF))的带隙修饰。通过合成和计算的结合,我们阐明了具有氨基化连接体的 MIL-125 的电子结构。当使用单氨基化 bdc-NH2 连接体时,观察到带隙减小,这是由于 N 2p 电子向芳族连接单元供体,导致 MIL-125 的价带边缘上方的带隙红移。我们进一步通过计算模拟了具有二氨基化连接体 bdc-(NH2)2 和其他官能团(-OH、-CH3、-Cl)的 MIL-125,作为控制光学响应的替代取代基。预测 bdc-(NH2)2 连接体将 MIL-125 的带隙降低到 1.28eV,这通过靶向合成基于 bdc-(NH2)2 的 MIL-125 得到了证实。这项研究说明了通过连接单元的合理功能化来调节 MOF 的光学响应的可能性,以及综合合成/计算方法对于靶向功能化混合材料的强大性。

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