Confinement‐Driven Photophysics in Hydrazone‐Based Hierarchical Materials
Confinement‐Driven Photophysics in Hydrazone‐Based Hierarchical Materials
复制标题
基于腙的限制驱动光物理分层材料
DOI：
10.1002/anie.202211776
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Wilson, Gina R.
中科院分区：
文献类型：
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作者：
Thaggard, Grace C.;Leith, Gabrielle A.;Sosnin, Daniil;Martin, Corey R.;Park, Kyoung Chul;McBride, Margaret K.;Lim, Jaewoong;Yarbrough, Brandon J.;Maldeni Kankanamalage, Buddhima K. P.;Wilson, Gina R.
限制施加的量子物理学探索了新的刺激响应性腙基化合物，首次证明了它们在2D与3D多孔基质中的行为的概念差异。与光开关异构化相关的挑战可以在3D材料中克服，这些挑战是由2D支架中的宿主与光致变色化合物的相互作用引起的。通过在3D支架中的配位固定，实现了固态空间要求高的腙衍生物的溶液样光异构化速率常数。根据稳态和时间分辨的光物理测量和理论建模，这种方法提供了在固态下具有快速光异构化动力学的基于腙的材料。集成的腙衍生物的快速异构化允许探测和定制作为激发波长的函数的共振能量转移（ET）过程，为ET调制提供了新的途径。
Confinement‐imposed photophysics was probed for novel stimuli‐responsive hydrazone‐based compounds demonstrating a conceptual difference in their behavior within 2D versus 3D porous matrices for the first time. The challenges associated with photoswitch isomerization arising from host interactions with photochromic compounds in 2D scaffolds could be overcome in 3D materials. Solution‐like photoisomerization rate constants were realized for sterically demanding hydrazone derivatives in the solid state through their coordinative immobilization in 3D scaffolds. According to steady‐state and time‐resolved photophysical measurements and theoretical modeling, this approach provides access to hydrazone‐based materials with fast photoisomerization kinetics in the solid state. Fast isomerization of integrated hydrazone derivatives allows for probing and tailoring resonance energy transfer (ET) processes as a function of excitation wavelength, providing a novel pathway for ET modulation.