El Haitami Alae, Resmerita Ana-Maria, Ursu Laura Elena, Asandulesa Mihai, Cantin Sophie, Farcas Aurica
Laboratory of Physical Chemistry of Polymers and Interfaces, CY Cergy Paris Université, F95000 Cergy, France.
"Petru Poni" Institute of Macromolecular Chemistry, Romanian Academy, Grigore Ghica Voda Alley, 41A, 700487 Iasi, Romania.
Materials (Basel). 2023 Jun 30;16(13):4757. doi: 10.3390/ma16134757.
Two poly(3,4-ethylenedioxythiophene) polyrotaxanes (PEDOT∙TMe-βCD and PEDOT∙TMe-γCD) end-capped by pyrene (Py) were synthesized by oxidative polymerization of EDOT encapsulated into TMe-βCD or TMe-γCD cavities with iron (III) chloride (FeCl) in water and chemically characterized. The effect of TMe-βCD or TMe-γCD encapsulation of PEDOT backbones on the molecular weight, thermal stability, and solubility were investigated in depth. UV-vis absorption, fluorescence (F), phosphorescence (P), quantum efficiencies, and lifetimes in water and acetonitrile were also explored, together with their surface morphology and electrical properties. Furthermore, dynamic light scattering was used to study the hydrodynamic diameter (DH) and z-potential (ZP-ζ) of the water soluble fractions of PEDOT∙TMe-βCD and PEDOT∙TMe-γCD. PEDOT∙TMe-βCD and PEDOT∙TMe-γCD exhibited a sharp monodisperse peak with a DH of 55 ± 15 nm and 122 ± 32 nm, respectively. The ZP-ζ value decreased from -31.23 mV for PEDOT∙TMe-βCD to -20.38 mV for PEDOT∙TMe-γCD, indicating that a negatively charged layer covers their surfaces. Surface pressure-area isotherms and Brewster angle microscopy (BAM) studies revealed the capability of the investigated compounds to organize into sizeable and homogeneous 2D supramolecular assemblies at the air-water interface. The control of the 2D monolayer organization through the thermodynamic parameters of PEDOT∙TMe-βCD and PEDOT∙TMe-γCD suggests potential for a wide range of optoelectronic applications.
通过在水中用三氯化铁（FeCl）对封装在TMe-β环糊精或TMe-γ环糊精腔内的3,4-乙撑二氧噻吩（EDOT）进行氧化聚合，合成了两种以芘（Py）封端的聚（3,4-乙撑二氧噻吩）聚轮烷（PEDOT∙TMe-βCD和PEDOT∙TMe-γCD），并对其进行了化学表征。深入研究了TMe-βCD或TMe-γCD对PEDOT主链的包封对分子量、热稳定性和溶解性的影响。还研究了它们在水和乙腈中的紫外-可见吸收、荧光（F）、磷光（P）、量子效率和寿命，以及它们的表面形态和电学性质。此外，使用动态光散射研究了PEDOT∙TMe-βCD和PEDOT∙TMe-γCD水溶性部分的流体动力学直径（DH）和z电位（ZP-ζ）。PEDOT∙TMe-βCD和PEDOT∙TMe-γCD分别呈现出尖锐的单分散峰，DH分别为55±15nm和122±32nm。ZP-ζ值从PEDOT∙TMe-βCD的-31.23mV降至PEDOT∙TMe-γCD的-20.38mV，表明它们的表面覆盖有带负电荷的层。表面压力-面积等温线和布鲁斯特角显微镜（BAM）研究表明，所研究的化合物能够在空气-水界面形成尺寸可观且均匀的二维超分子组装体。通过PEDOT∙TMe-βCD和PEDOT∙TMe-γCD的热力学参数对二维单层组织进行控制，显示出在广泛的光电子应用中的潜力。
