Host and guest joining forces: a holistic approach for metal?organic frameworks in nonlinear optics
Host and guest joining forces: a holistic approach for metal?organic frameworks in nonlinear optics
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主宾联手：非线性光学中金属有机框架的整体方法
DOI：
10.1039/d2tc01075e
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发表时间：
2022
影响因子：
6.4
通讯作者：
Uji-i Hiroshi
中科院分区：
文献类型：
--
作者：
Wolf Mathias;Hirai Kenji;Toyouchi Shuichi;Daelemans Brent;Fron Eduard;Uji-i Hiroshi
金属有机骨架（MOFs）在非线性光学（NLO）领域有着广泛的应用前景。然而，目前用于NLO中的M0 F的设计策略通常限于工程化M0 F本身或使用M0 F在其孔内对准NLO活性分子。但是在设计MOFs和选择客体分子时可以考虑更多的设计因素。可以组合主机和客户的NLO发射，而不是仅使用两者中的任一者。主体和客体之间的相互作用可以是通过改变对称性、偶极矩、键长、电荷分布等进一步改进的来源。此外，不稳定的NLO分子可以通过在MOF中的调节而潜在地稳定。在这里，我们通过将MOF-177作为主体和Li@C60作为NLO的客体组合来展示MOF的新策略，这意味着MOF本身以及客体分子都发射NLO信号，并且使用它们在MOF内的相互作用延长键进一步增加发射，从而充分利用MOF的二次谐波产生潜力。使用这种方法，与单独使用M0 F-177相比，总排放量可以提高40%。此外，进入M0 F-177的调节使Li@C60稳定，Li@C60通常在没有反离子的环境条件下不稳定。
Metal–organic frameworks (MOFs) are interesting candidates for applications in nonlinear optics (NLO). However, current design strategies for MOFs in NLO are typically limited to either engineering the MOF itself or using the MOF to align NLO-active molecules within its pores. But more design factors can be considered when engineering MOFs and choosing guest molecules. The NLO emission of the host and guests can be combined instead of using only either one of the two. The interaction between the host and guest can be a source for further improvement by changing the symmetry, dipole moment, bond lengths, charge distribution, etc. Additionally, unstable NLO molecules can potentially be stabilized by accommodation in the MOF. Here, we demonstrate a new strategy for MOFs by combining MOF-177 as a host and Li@C60 as a guest for NLO, meaning that both the MOF itself as well as the guest molecules are emitting NLO signals, as well as further increasing the emission using their interaction elongating bonds within the MOF, thus fully using the MOF's potential for second harmonic generation. Using this approach, the overall emission can be boosted by 40% compared to MOF-177 alone. Furthermore, the accommodation into MOF-177 stabilizes Li@C60 that is normally unstable under ambient conditions without a counterion.