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, Hill Austin R, Smith Mark D, Garashchuk Sophya, Greytak Andrew B, Aprahamian Ivan, Shustova Natalia B
Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC 29208, USA.
Department of Chemistry, Dartmouth College, Hanover, NH 03755, USA.
Angew Chem Int Ed Engl. 2023 Jan 9;62(2):e202211776. doi: 10.1002/anie.202211776. Epub 2022 Dec 2.
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.
首次对基于腙的新型刺激响应化合物进行了受限光物理研究，结果表明它们在二维和三维多孔基质中的行为存在概念上的差异。在三维材料中，可以克服二维支架中主体与光致变色化合物相互作用引起的光开关异构化相关挑战。通过将空间位阻较大的腙衍生物配位固定在三维支架中，实现了固态下类似溶液的光异构化速率常数。根据稳态和时间分辨光物理测量以及理论建模，该方法能够制备出固态下具有快速光异构化动力学的基于腙的材料。整合的腙衍生物的快速异构化能够探测和调节作为激发波长函数的共振能量转移（ET）过程，为ET调制提供了一条新途径。
