Hydrogen bonding: a mechanism for tuning electronic and optical properties of hybrid organic–inorganic frameworks (氢键连接：有机-无机杂化框架的电子和光学性质的调控机制)

Fedwa El-Mellouhi, El Tayeb Bentria, Asma Marzouk, Sergey N Rashkeev, Sabre Kais & Fahhad H Alharbi
npj Computational Materials 2, Article number: 16035 (2016)
doi:10.1038/npjcompumats.2016.35
Published online:04 November 2016
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摘要：无机-有机杂化框架材料领域是材料科学中发展最快的领域之一，因其丰富的结构和化学多样性可通过多种技术赋予材料一些奇特的性能。这其中最重要的就是通过改变它们的化学、制造技术和制备条件，来调控这类复杂材料的结构、光学、热学、机械和电子方面的性能。本研究通过引入结构单元以与环境物质形成氢键而实现调控，因而在这一领域内取得了显著进展。考虑到杂化框架材料的各种有序结构中含质子化的锍阳离子H3S+和带负电的卤素阴离子(I?、Br?、Cl?和F?)，我们发现氢键链接增加了材料的结构稳定性，从而有可能用于调控带隙附近的电子态。本研究认为，这样通过氢键连接调控有着普遍意义，在质子化阳离子无机-有机杂化框架材料中可观察到，可在光电和光伏应用方面发挥作用。

Abstract: The field of hybrid inorganic–organic framework materials is one of the fastest growing fields in materials science because their enormous structural and chemical diversity presents great opportunities for creating many technologically relevant properties. One of the most important issues is controlling and tuning the structural, optical, thermal, mechanical and electronic properties of these complex materials by varying their chemistry, fabrication techniques and preparation conditions. Here we demonstrate that significant progress in this area may be achieved by introducing structural elements that form hydrogen bonds with the environment. Considering hybrid framework materials with different structural ordering containing protonated sulfonium cation H3S+ and electronegative halogen anions (I?, Br?, Cl? and F?), we found that hydrogen bonding increases the structural stability of the material and may be used for tuning electronic states near the bandgap. We suggest that such a behaviour has a universal character and should be observed in hybrid inorganic–organic framework materials containing protonated cations. This effect may serve as a viable route for optoelectronic and photovoltaic applications.