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Updated: Nov 11, 2025

Interfacial Molecular-level Structures of Polymers and Biomacromolecules Revealed via Sum Frequency Generation Vibrational Spectroscopy
Published on: August 13, 2019
Unlocking the Remarkable Influence of Intramolecular Group Rotation for Third-order Nonlinear Optical Properties
Kangshuai Geng1, Qiong Xie1, Yujie Zhao1
1Green Catalysis Center and College of Chemistry, Zhengzhou University, 450001, Zhengzhou, P. R. China.
Abstract:
This work exposes for the first time the remarkable influence of intramolecular group rotation on third-order nonlinear optical (NLO) performance. In order to prove the role of group rotation, we designed and synthesized two photo-response compounds tetramethyl 5,5'-(((diazene-1,2-diylbis(4,1-phenylene))bis(oxy))bis(methylene))diisophthalate (1) and 5,5'-(((diazene-1,2-diylbis(4,1-phenylene))bis(oxy))bis(methylene))diisophthalic acid (2) and investigated their NLO performance under different substituent (benzyloxy group) rotation states. 1 and 2 have dynamic benzyloxy group rotation in dilute solution and shows reverse saturated absorption (RSA). When the benzyloxy group rotation of 1 and 2 was restricted by PMMA, their NLO performance not only converted into saturated absorption (SA) and NLO refraction behaviours, but also hardly changed after isomerization. Interestingly, we also restricted the benzyloxy group rotation in solution to a certain extent through photo-induced trans→cis isomerization, and found that the NLO performances of cis isomers of 1 and 2 exhibit SA and positive refraction and are similar to those of 1-PMMA and 2-PMMA. This work provides a new exploratory method for studying the influencing factors of third-order NLO performance.
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