Engineering the Optical Response of the Titanium-MIL-125 Metal-Organic Framework through Ligand Functionalization
Engineering the Optical Response of the Titanium-MIL-125 Metal-Organic Framework through Ligand Functionalization
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DOI：
10.1021/ja405350u
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发表时间：
2013-07-31
影响因子：
15
通讯作者：
Walsh, Aron
中科院分区：
文献类型：
--
作者：
Hendon, Christopher H.;Tiana, Davide;Walsh, Aron
在这里，我们讨论了带隙改性的MIL-125，一个TiO 2/1，4-苯二甲酸（bdc）金属有机框架（MOF）。通过合成和计算相结合，我们阐明了MIL-125与胺化连接的电子结构。当使用单胺化bdc-NH 2连接体时观察到的带隙减小是由于N 2 p电子捐赠给芳族连接单元，导致MIL-125的价带边缘以上的红移带。我们进一步在计算机上探索了具有二胺化连接基bdc（NH 2）（2）和其他官能团（-OH、-CH 3、-Cl）作为替代取代基的MIL-125，以控制光学响应。预测bdc-（NH 2）2连接单元将MIL-125的带隙降低至1.28 eV，并且这通过基于bdc-（NH 2）（2）的MIL-125的靶向合成得到证实。这项研究说明了通过合理的官能化的连接单元，和强度的组合合成/计算方法的目标功能化的杂化材料的MOFs的光学响应调谐的可能性。
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.