Synthesis And Aggregates Study On Self-Assembly Of Amphiphilic Rod-Coil Molecules

Self-assembly of amphiphilic block rod-coil molecules are widely studied due to their remarkable application prospects as a good light, electricity, functional magnetic advanced functional nanomaterials and molecular devices. In this paper, three series of amphiphilic rod-coil molecules were designed successfully synthesized, the molecular structures are characterized by1H-NMR and MALDI-TOF-MASS spectroscopy. The self-assembling behaviors of these molecules were investigated by means of differential scanning calorimetry (DSC), polarizing optical microscopy (POM), X-Ray diffraction (XRD), Dynamic light scattering (DLS), UV-vis absorption spectroscopy, the steady-state fluorescence spectra and scanning electron microscopy (SEM) in bulk state and solution.Firstly, two diblock rod-coil aromatic amphiphilic molecule, consisting of three biphenyls and one styrene unit linked together with ether bonds as a rigid rod segment, and poly(ethylene oxide) with the number of repeating units of 22 (5a)and 34(5b) as coil segment have been synthesized.The self-assembling behaviors of them are also investigated.The result indicates that the molecule 5a has one liquid crystalline mesophase and 5b have no liquid crystalline phase, the X-ray scattering experiments prove that molecule 5b spontaneously self-assembles into lamellar structure in the crystalline phase. In aqueous medium, the two molecules self-assemble into discretely cylindrical and ordered spherical aggregates respectively, the aggregates can be used as nanoreactor for Suzuki coupling reaction at room temperature.Secondly, we introduce the synthesis and self-assembly property of terpyridine and its complex (10 and 11). In bulk state, the molecule 10 self-assembles into 3-D hexagonal perforated layer crystalline phase at room temperature, and this molecule ia able to self-assemble into well-organized cylindrical micelle aggregates in solution. The molecule 11self-assembles into 1-D lamellar stucture at room temperature and self-assembles into well-organized spherical micelle aggregates in solution. Meanwhile, the color of light-emission can be modulated from violet to cyan in solution 10 and 11, which reveals complexation has significant effect on the optical properties of molecules.For amphiphilic triblock cruciform compounds (1,2,3), we mainly introduce on the synthesis and self-assembly propertyies, the results show that in the bulk state, all of them have a liquid crystalline mesophase, at the same time, the compound 1 and 2 self-assemble into nematic stucture in the liquid crystal phase while compound 3 self-assembles into columnar phase. Their solid-state structure and solution-phase assembly performance need further study.