Tian Yi-Bo, Li Qiao-Hong, Wang Zirui, Gu Zhi-Gang, Zhang Jian
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002, Fuzhou, P. R. China.
Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), 76344, Eggenstein-Leopoldshafen, Germany.
Nano Lett. 2023 Apr 12;23(7):3062-3069. doi: 10.1021/acs.nanolett.3c00635. Epub 2023 Mar 30.
Structural asymmetry affecting the nonlinear optics (NLO) of metal-organic frameworks (MOFs) is very important in fundamentals and applications but is still a challenge. Herein we develop a series of indium-porphyrinic framework (InTCPP) thin films and provide the first study on the coordination-induced symmetry breaking on their third-order NLO. The continuous and oriented InTCPP(H) thin films were grown on quartz substrates and then postcoordinated with different cations (Fe or FeCl) in InTCPP(H) (named InTCPP(Fe) and InTCPP(FeCl)). The third-order NLO results reveal the Fe and FeCl coordinated InTCPP thin films have substantially enhanced NLO performance. Moreover, InTCPP(FeCl) thin films cause symmetry breaking of microstructures, resulting in a 3-fold increase in the nonlinear absorption coefficient (up to 6.35 × 10 m/W) compared to InTCPP(Fe). This work not only develops a series of nonlinear optical MOF thin films but also provides new insight into symmetry breaking on MOFs for nonlinear optoelectronic applications.
影响金属有机框架（MOF）非线性光学（NLO）的结构不对称性在基础研究和应用中都非常重要，但仍然是一个挑战。在此，我们制备了一系列铟卟啉框架（InTCPP）薄膜，并首次对其三阶NLO中配位诱导的对称性破缺进行了研究。连续且取向的InTCPP(H)薄膜生长在石英衬底上，然后在InTCPP(H)中与不同阳离子（Fe或FeCl）进行后配位（分别命名为InTCPP(Fe)和InTCPP(FeCl)）。三阶NLO结果表明，Fe和FeCl配位的InTCPP薄膜具有显著增强的NLO性能。此外，InTCPP(FeCl)薄膜导致微观结构的对称性破缺，与InTCPP(Fe)相比，非线性吸收系数增加了3倍（高达6.35×10 m/W）。这项工作不仅制备了一系列非线性光学MOF薄膜，还为非线性光电子应用中MOF的对称性破缺提供了新的见解。
