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Postsynthetic Framework Contraction Enhances the Two-Photon Absorption Properties of Pillar-Layered Metal–Organic Frameworks
Chemistry of Materials ( IF 7.2 ) Pub Date : 2020-06-09 , DOI: 10.1021/acs.chemmater.0c01417
David C. Mayer 1 , Jan K. Zarȩba 2 , Gabriele Raudaschl-Sieber 1 , Alexander Pöthig 1 , Marta Chołuj 3 , Robert Zaleśny 3 , Marek Samoć 2 , Roland A. Fischer 1
Affiliation  

Aggregation-induced emission (AIE) dyes have been shown to be a potential ligand class for multiphoton absorbing metal–organic frameworks (MPA-MOFs); however, the influence of framework flexibility on the local ligand conformation and its ramifications on the nonlinear absorption properties of this material class have sparsely been understood. In this study, we systematically investigate the two-photon absorption properties of two pillar-layered MOFs comprising tetraphenylethylene AIE ligands and compare the results to the organic ligand in crystal form, using a combination of linear and nonlinear optical characterization methods and electronic-structure calculations. We demonstrate that self-confining the AIE ligand is key to enhance the nonlinear optical absorption properties, as a structure transformation to contracted frameworks strongly increases the two-photon absorption response, which can be addressed by specific ligand substitution. Our results have important implications on the design of MPA-MOFs and provide synthetic guidelines not only from a fundamental point of view but also application-wise.

中文翻译:

后合成框架收缩增强了层状金属有机框架的双光子吸收特性

聚集诱导发射(AIE)染料已被证明是多光子吸收金属-有机骨架(MPA-MOF)的潜在配体类别。然而,人们对骨架柔性对局部配体构象及其分支对这类材料的非线性吸收性质的影响的了解很少。在这项研究中,我们系统地研究了包含四苯基乙烯AIE配体的两个柱状层状MOF的双光子吸收特性,并使用线性和非线性光学表征方法以及电子结构计算的结果,将结果与晶体形式的有机配体进行了比较。 。我们证明自约束AIE配体是增强非线性光学吸收特性的关键,由于结构向收缩框架的转化极大地增加了双光子吸收响应,这可以通过特定的配体取代来解决。我们的结果对MPA-MOF的设计具有重要意义,不仅从基本的角度而且在应用方面提供了综合指导。
更新日期:2020-07-14
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