Synthesis and Structural Analysis of Coil-Rod-Coil Molecules Containing Lateral Groups in the Middle of the Rod Segment†

doi:10.7503/cjcu20150490

Abstract

Abstract:

A series of triblock coil-rod-coil molecules, containing biphenyl, phenyl and phenyl groups with lateral units linked together with ether as a rod segment and poly(ethylene oxide)(PEO) which have a polymerization degree of 7, 12, 17, as the coil segment, was synthesized. Molecular structures of these compounds were characterized by means of ¹H NMR and MALDI-TOF MS. The self-assembling behavior of the molecules was investigated by means of differential scanning calorimetry(DSC), small-angle X-ray scattering(SAXS) and optical polarized micrograph(POM) in the bulk state. The molecules 1a—1c spontaneously self-assembled into lamellar, hexagonal perforated lamellar, oblique columnar structure, while molecules 2a—2c self-assembled into oblique columnar and body-centered tetragonal structures in the crystalline phase, respectively. The results revealed that the lateral groups attached to the middle of rod segments dramatically influence the self-assembling behavior of these rod-coil molecular system.

Key words: Body-centered tetragonal, Self-assemble, Columnar phase, X-Ray scattering

CLC Number:

O625.52⁺3

TrendMD:

YANG Yuntian, YU Shengsheng, LI Zhaohua, CHEN Tie, JIN Longyi. Synthesis and Structural Analysis of Coil-Rod-Coil Molecules Containing Lateral Groups in the Middle of the Rod Segment^†[J]. Chem. J. Chinese Universities, 2016, 37(1): 48.

Figures/Tables 6

Scheme 1 Synthetic routes of compounds 1a—1c and 2a—2c

Fig.1 DSC traces recorded during the heating and the cooling scans(10 ℃/min) ^HPL: hexagonal perforated lamellar phase; ob: oblique columnar phase; tet: body-centered tetragonal; i: isotropic. (A)—(C) Compounds 1a—1c; (D)—(F) compounds 2a—2c.

Fig.2 Representative optical polarized micrographs(40×) of the textures^ (A) Hexagonal perforated lamellar structure of compound 1a; (B) oblique columnar structure of compound 1b in the liquid crystalline phase.

Fig.3 Small-angle XRD patterns of compounds 1a—1c at different temperatures^ (A) Compound 1a at 70 ℃; (B) compound 1a at 125 ℃; (C) compound 1b at 67 ℃; (D) compound 1b at 72 ℃; (E) compound 1c at 30 ℃.

Fig.4 Small-angle XRD patterns of compounds 2a—2c at different temperatures^ (A) Compound 2a at 100 ℃; (B) compound 2a at 120 ℃; (C) compound 2b at 50 ℃; (D) compound 2b at 90 ℃; (E) compound 2c at 110 ℃.

Fig.5 Schematic representation of self-assembly^ (A) Layer structure for compound 1a; (B) hexagonal perforated layer structure for compound 1a; (C) oblique columnar structure for compound 2b; (D) body-centered tetragonal micellar structure for compound 2b.

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