Design, Synthesis and Second‐Order Nonlinear Optical Properties of Azobenzene‐Based Polysiloxanes

Author:

Tong Xingwen1,Zheng Xunsheng2,Zhao Zhennan1,Li Quanwei1,Zhao Haisong1,Zou Dexun2ORCID,Ren Zhongjie1

Affiliation:

1. State Key Laboratory of Chemical Resource Engineering Beijing University of Chemical Technology Beijing 100029 China

2. Department of Environmental Science and Engineering Beijing University of Chemical Technology Beijing 10029 China

Abstract

AbstractTo study the effect of polymeric structures on second‐order nonlinear optical properties, polysiloxanes materials based on azobenzene as chromophore have been designed and synthesized successfully. Herein, the siloxane monomer is directly bonded to azobenzene units by palladium catalysis, which avoids the influence of flexible chains on the photoelectric properties of azobenzene. According to the different positions of azobenzene units in the polymers, it is divided into side‐chain, main‐chain, and alternative‐type polymers. The chemical structures of obtained polysiloxanes are confirmed by nuclear magnetic resonance spectra and mass spectra. Three polymers present high thermal decomposition temperatures and the medium glass transition temperatures. The effects of polymeric structures on the second‐order nonlinear properties are compared. The main‐chain polysiloxane possesses the highest thermal stability because of its rigid architecture. The side‐chain polysiloxane shows the fastest isomerization transformation rate due to the large free volume. Besides, the alternative polysiloxane displays the best second‐order nonlinear performance with second harmonic generation coefficient (d33) value of 47.6 pm V−1, which is 3 times higher than the side‐chain one.

Funder

National Natural Science Foundation of China

Natural Science Foundation of Shandong Province

Publisher

Wiley

Subject

Materials Chemistry,Polymers and Plastics,Organic Chemistry

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