Wansheng Zong,Lixin Wang,Qing Guo,Juan Li,Wenbo Wu,Yingliang Liu,Shengang Xu,Shaokui Cao
A hyper-structured molecule (HSM) CRA-DR1 and a model molecule Ph-DR1 for photorefractive (PR) application under non-electric field were designed and synthesized via highly reactive “click” reaction between alkynyl derivatives of calix [4]resorcinarene (CRA) or resorcinol and an azide derivative of disperse red 1 (DR1) in satisfactory yields. XRD pattern and UV–Vis absorption spectra indicated that the CRA-DR1 with three-dimensional (3D) CRA core could effectively decrease the aggregation, packing and crystallization of the nonlinear optical (NLO) chromophores . AFM images showed a smooth and pinhole-free morphology of the CRA-DR1 film. Two-beam coupling (TBC) experiment was used to test the photorefractive performance in optically transparent films of Ph-DR1 and CRA-DR1 doped with [6,6]-phenyl-C 61 -butyric acid methyl ester (PCBM) as a photosensitizer and N -ethyl-carbazole (ECz) as a plasticizer . Without poling and without external electric filed, the coupling gain coefficient obtained in the CRA-DR1-based composite is 147.4 cm −1 , which is higher than that of Ph-DR1-based composite (132.6 cm −1 ) owing to its asymmetrical 3D CRA core. Coupled with its convenient synthesis and commercial DR1, CRA-DR1 could serve as a good candidate for PR application.
Carbazole-based bi-functional photorefractive polyacrylates were prepared via free radical polymerization and post-azo-coupling reaction. The structure of polymers was characterized by Fourier transform infrared spectroscopy (FTIR) and proton nuclear magnetic resonance ( 1 H-NMR) spectroscopy. The differential scanning calorimetry (DSC) and the thermal gravimetric analysis (TGA) were used to characterize the thermal property of polymers. The results indicate that though the glass transition temperature ( T
g ) of polymers increases with increasing the ratio of NLO groups, the polymers with different ratios of NLO groups still all show low glass transition temperatures around 60 °C, and good thermal stability, which are favorable to the practical application of these polymers. The gel permeation chromatographic (GPC) result indicates that these polymers all have high-molecular-weight which is favorable to the long term stability of the material. Further, these polymers have good solubility in chloroform solvent, and the solutions can easily be fabricated into optically transparent films. Gain coefficients of 75 cm −1 , 185 cm −1 and 66 cm −1 can be observed at zero external electric field without any addition agent or pre-poling for polymers P-2, P-3 and P-4 respectively. The different contents of NLO groups result in the different properties of polymers P-2, P-3 and P-4.
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