Synthesis and Self-assembly of Triblock Oligomers Containing Anthracene Unit†

doi:10.7503/cjcu20130817

Abstract

Abstract:

Rod-coil molecules, consisting of a flexible and a rigid block, have a strong tendency to self-organize into a various supramolecular nanostructures in the bulk state. Coil-rod-coil triblock cruciform compounds 1 and 2 incorporating anthracene unit were synthesized through Sonogashira coupling reaction. Molecular structures of these compounds were characterized by ¹H NMR and MALDI-TOF mass spectroscopy. The self-assembling behaviors of these molecules were investigated by means of differential scanning calorimetry(DSC), thermal polarized optical microscopy(POM), small-angle and wide-angle X-ray scattering(SAXS and WAXS) at the bulk state. In liquid crystalline mesophase, compounds 1 connecting with poly(ethylene oxide)(PEO) as flexible chains self-assembles into oblique columnar phase(Col_o) and nematic phase, while compound 2 containing alkyl flexible chain self-assembles into lamellar structure(L) in the solid state, and has not shown liquid crystalline phase.

Key words: Rod-coil molecule, Self-assembly, Anthracene unit, Cruciform

CLC Number:

O625.15⁺4

TrendMD:

LIU Yang, ZHU Jikai, WANG Zhuoshi, ZHONG Keli, JIN Guangri, CHEN Tie, JIN Longyi. Synthesis and Self-assembly of Triblock Oligomers Containing Anthracene Unit^†[J]. Chem. J. Chinese Universities, 2014, 35(5): 989.

Figures/Tables 5

Scheme 1 Synthetic routes of compounds 1 and 2

Fig.1 Representative optical polarized micrographs of the texture exhibited by nematic phase at 120 ℃(A) and oblique columnar structure at 78 ℃(B) for compound 1 from the isotropic liquid cooling to the liquid crystalline phase^(A) ×40; (B) ×20.

Fig.2 Small-angle X-ray scattering patterns of compounds 1(a) and 2(b) measured in melt state and solid state plotted against q^q=4πsinθ/λ. (A) Oblique columnar phase for compound 1 at 80 ℃, (B) lamellar phase for compound 2 at 180 ℃.

Table 1 Small-angle X-ray scattering data for oblique columnar structure of compound 1 in the liquid crystalline phase(measured at 80 ℃)*

h	k	q_obs./nm^-1	q_calcd./nm^-1	h	k	l	q_obs./nm^-1	q_calcd./nm^-1
1	0	1.378	1.378	2	1	0	2.754	2.754
1	1	2.142	2.139	2	0	0	2.982	2.998
0	1	2.341	2.341

Fig.3 Schematic representation for the formation of nematic phase(A), oblique columnar structure for compound 1 in the liquid crystalline phase(B) and lamellar structure for compound 2 in the solid state(C)

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