Designed synthesis and chiroptical properties of regioregular poly(<italic>p</italic>-phenyleneethynylene-alter-m-phenyleneethynylene) bearing (-)-trans-myrtanoxyl side groups

doi:10.1007/s11458-009-0018-7

Front Chem Chin

2009, Vol. 4

Issue (1) : 93-103 https://doi.org/10.1007/s11458-009-0018-7

RESEARCH ARTICLE

Designed synthesis and chiroptical properties of regioregular poly(p-phenyleneethynylene-alter-m-phenyleneethynylene) bearing (-)-trans-myrtanoxyl side groups

Xiangfeng LI, Chusheng LI, Jiang LU, Hui LIANG(

)

School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China

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Abstract

Two regioregular poly(p-phenyleneethynylene-alter-m-phenyleneethynylene)s bearing (-)-trans-myrtanoxyl side groups with different substitution patterns were designed and synthesized, e.g. Myr-PMPE-1 and Myr-PMPE-2. In Myr-PMPE-1, the side chiral groups are distributed uniformly along the backbone. In Myr-PMPE-2, the distribution of the side chiral groups is alternatively crowded and loose. Both of these two polymers show no CD signal in solutions because of their good solubility. The investigations of chiroptical properties of these two polymers were carried out in the form of spin-coated films. The films were annealed above the glass temperature of the corresponding polymer, and the effects of annealing temperature and time on the properties of the films were investigated by UV-Vis absorption, fluorescence and circular dichroism spectra. The results show that annealing treatment had no significant effect on the properties of Myr-PMPE-1, including UV-Vis absorption, fluorescence and optical activity. The maximum absolute value of dissymmetry factor (|g_max|) was 1.62 × 10^-4. On the other hand, annealing treatment significantly affected the properties of Myr-PMPE-2. Without annealing or being annealed below 100°C, Myr-PMPE-2 films show almost no Cotton effect. In contrast, when annealed above 120°C, the absorption and emission of Myr-PMPE-2 films slightly red shifted with increasing annealing temperature and annealing time. Most importantly, the intensity of CD signals increased significantly and the optical activity of Myr-PMPE-2 films markedly increased. After annealing at 140°C for 4 h, the |g_max| of Myr-PMPE-2 films was increased up to 3.07 × 10^-3, about one order of magnitude higher than that of Myr-PMPE-1 films.

Keywords chiral conjugated polymer optical activity circular dichroism

Corresponding Author(s): LIANG Hui,Email:ceslhui@mail.sysu.edu.cn

Issue Date: 05 March 2009

Cite this article:

Xiangfeng LI,Chusheng LI,Jiang LU, et al. Designed synthesis and chiroptical properties of regioregular poly(p-phenyleneethynylene-alter-m-phenyleneethynylene) bearing (-)-trans-myrtanoxyl side groups[J]. Front Chem Chin, 2009, 4(1): 93-103.

URL:

https://academic.hep.com.cn/fcc/EN/10.1007/s11458-009-0018-7
https://academic.hep.com.cn/fcc/EN/Y2009/V4/I1/93

Fig.1 Synthetic strategy of chiral regioregular poly(-phenyleneethynylene-alter- m-phenyleneethynylene)

Fig.2 Different linking patterns of monomer units in irregular polymer

Fig.3 H-NMR spectra of compound 9 () and Myr-PMPE-1 ()

Fig.4 H-NMR spectra of compound 10 () and Myr-PMPE-2()

Fig.5 Comparison of the molecular structures of Myr-PMPE-1 and Myr-PMPE-2

Fig.6 TGA curves of Myr-PMPE-1 and Myr-PMPE-2

Fig.7 DSC curves of Myr-PMPE-1 and Myr-PMPE-2

Fig.8 Effect of annealing on the UV-Vis spectra of Myr-PMPE-1 film() Original; () Normalized

Fig.9 Normalized emission spectra of a Myr-PMPE-1 spin-coated films before and after annealing, excited at 383 nm

Fig.10 CD spectra of Myr-PMPE-1 spin-coated films annealed at different temperatures

Fig.11 Effect of annealing on the UV-Vis spectra of Myr-PMPE-2 films
() Original; () Normalized

Fig.12 Normalized emission spectra of Myr-PMPE-2 spin-coated films before 4 and after annealing, excited at 398 nm

Fig.13 CD spectra of a Myr-PMPE-2 spin-coated film on glass after annealing

Tab.1 Effect of annealing on the of Myr-PMPE-1 and Myr-PMPE-2

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