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. 2018 Jan 3;8(2):1014-1021.
doi: 10.1039/c7ra12652b. eCollection 2018 Jan 2.

Synthesis, chiroptical properties, and self-assembled nanoparticles of chiral conjugated polymers based on optically stable helical aromatic esters

Chao Zhang  1 , Meng Li  2 , Hai-Yan Lu  1 , Chuan-Feng Chen  1   2
Affiliations

Synthesis, chiroptical properties, and self-assembled nanoparticles of chiral conjugated polymers based on optically stable helical aromatic esters

Chao Zhang et al. RSC Adv. .

Abstract

By Suzuki coupling reaction, three pairs of chiral conjugated polymers with optically stable helical aromatic ester subunits as the main-chain were designed and synthesized. Polymers (+)-P-P1 and (-)-M-P1, (+)-P-P2 and (-)-M-P2 showed strong fluorescence emission, strong mirror image CD and circularly polarized luminescence (CPL) signals in THF. For polymers (+)-P-P3 and (-)-M-P3, containing the tetraphenylethene (TPE) moiety, they not only showed obvious aggregation induced enhancement emission (AIEE), but also exhibited mirror image CD signals and aggregation-induced enhancement CPL signals in THF-water mixtures. Moreover, (+)-P-P3 and (-)-M-P3 could also form chiral nanoparticles by solvent evaporation induced self-assembly. Interestingly, it was further found that the size of the nanoparticles could be controlled by the changing of THF/water ratio, and their CPL properties were also shown.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. Synthesis of chiral conjugated polymers (+)-P-P1–3 and (−)-M-P1–3. M1: 2,2′-bithiophene-5,5′-diboronic acid bis(pinacol) ester; M2: 4,4′-biphenyldiboronic acid bis(pinacol) ester; M3: 1,2-diphenyl-1,2-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)ethane; M4 was obtained by the literature's method. Conditions: (i) DMF (3 mL), toluene (2 mL), Pd(PPh3)4 (0.1 equiv.), K2CO3 (8 equiv.), 110 °C.
Fig. 1
Fig. 1. (a) UV-vis spectra of (+)-P-P1–3 in THF. (b) Fluorescence spectra of (+)-P-P3 in THF–water mixtures. (c) Plot of (I/I0) values of (+)-P-P3versus the compositions of the aqueous mixtures. (d) Images of (+)-P-P3 in THF–water under 365 nm UV lamp. c = 1.0 × 10−4 M corresponding to the helical aromatic esters moiety.
Fig. 2
Fig. 2. (a) CD spectra of (+)-P-P1 and (−)-M-P1 in THF; (b) CD spectra of (+)-P-P2 and (−)-M-P2 in THF; (c) CPL spectra of (+)-P-P1 and (−)-M-P1 in THF; (d) CPL spectra of (+)-P-P2 and (−)-M-P2 in THF. c = 1.0 × 10−4 M corresponding to the helical aromatic esters moiety.
Fig. 3
Fig. 3. (a) CD spectra of (+)-P-P3 and (−)-M-P3 in THF–water mixtures; (b) CPL spectra of (+)-P-P3 and (−)-M-P3 in THF and THF–water mixtures (v/v, 20/80). c = 1.0 × 10−4 M corresponding to the TPE moiety.
Fig. 4
Fig. 4. SEM images of the nanoparticles self-assembled by (a) (+)-P-P3 and (b) (−)-M-P3 from THF–water (v/v, 40/60); (c) (+)-P-P3 and (d) (−)-M-P3 from THF–water (v/v, 20/80).
Fig. 5
Fig. 5. UV-vis spectra and fluorescence spectra of the nanoparticles assembled by (+)-P-P3.
Fig. 6
Fig. 6. (a) CD spectra and (b) CPL spectra of the nanoparticles assembled by (+)-P-P3 and (−)-M-P3. The self-assembled nanoparticles were obtained from THF–water (20/80, v/v).
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