Developing two-dimensional (2D) hybrid nanosheet arrays integrating inorganic and organic components is highly significant for third-order nonlinear optical (NLO) applications. Herein, an oriented 2D porphyrin-based MOF (ZnTPyP(Co)) thin film composed of vertically stacked ultrathin nanosheets was fabricated via the liquid-phase epitaxial (LPE) layer-by-layer (LBL) method. The prepared ZnTPyP(Co) thin film exhibits an outstanding third-order NLO response with a high third-order nonlinear susceptibility of ∼2.63 × 10^–7 esu, which is ascribed to the hybrid nanosheet array structure. Additionally, experimental Z-scan measurement and theoretical calculations also demonstrate that the substitution of Co metal ions in the porphyrinic core can increase the level of delocalization of the porphyrinic group and contribute to the material’s enhanced NLO properties. These findings not only provide new film candidates for NLO application but also highlight the potential of 2D MOF nanosheets in advanced optical devices.

中文翻译：

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一种基于卟啉的 MOF 薄膜，具有定向纳米片阵列，用于优化非线性光响应


开发集成无机和有机成分的二维 （2D） 混合纳米片阵列对于三阶非线性光学 （NLO） 应用具有重要意义。在此，通过液相外延 （LPE） 逐层 （LBL） 方法制造了由垂直堆叠的超薄纳米片组成的定向 2D 卟啉基 MOF （ZnTPyP（Co）） 薄膜。制备的 ZnTPyP（Co） 薄膜表现出出色的三阶 NLO 响应，具有 ∼2.63 × ^10-7 esu 的高三阶非线性磁化率，这归因于混合纳米片阵列结构。此外，实验 Z 扫描测量和理论计算还表明，卟啉核心中 Co 金属离子的取代可以增加卟啉基团的离域水平，并有助于增强材料的 NLO 性能。这些发现不仅为 NLO 应用提供了新的候选薄膜，而且突出了 2D MOF 纳米片在先进光学器件中的潜力。