Kochervinskii Valentin V, Gradova Margaret A, Gradov Oleg V, Sergeev Andrey I, Lobanov Anton V, Buryanskaya Evgeniya L, Ilina Tatiana S, Kiselev Dmitry A, Malyshkina Inna A, Kirakosyan Gayane A
Laboratory of Polymer Composite Materials, JSC Scientific Research Institute of Chemical Technology, Moscow 111524, Russia.
N.N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, Moscow 119991, Russia.
Nanomaterials (Basel). 2023 Jan 30;13(3):564. doi: 10.3390/nano13030564.
Polymer films doped by different porphyrins, obtained by crystallization from the acetone solutions, differ in absorption and fluorescence spectra, which we attribute to the differences in the structuring and composition of the rotational isomers in the polymer chains. According to the infrared spectroscopy data, the crystallization of the films doped with tetraphenylporphyrin (TPP) proceeds in a mixture of α- and γ-phases with TGTG and TGTG conformations, respectively. Three bonds in the planar zigzag conformation ensures the contact of such segments with the active groups of the porphyrin macrocycle, significantly changing its electronic state. Structuring of the films in the presence of TPP leads to an increase in the low-voltage AC-conductivity and the registration of an intense Maxwell-Wagner polarization. An increased conductivity by an order of magnitude in TPP-doped films was also observed at high-voltage polarization. The introduction of TPP during the film formation promotes the displacement of the chemical attachment defects of "head-to-head" type in the monomeric units into the surface. This process is accompanied by a significant increase in the film surface roughness, which was registered by piezo-force microscopy. The latter method also revealed the appearance of hysteresis phenomena during the local piezoelectric coefficient measurements.
通过从丙酮溶液中结晶获得的、由不同卟啉掺杂的聚合物薄膜,其吸收光谱和荧光光谱存在差异,我们将此归因于聚合物链中旋转异构体的结构和组成差异。根据红外光谱数据,掺杂四苯基卟啉(TPP)的薄膜结晶分别在具有TGTG和TGTG构象的α相和γ相混合物中进行。平面锯齿构象中的三个键确保了此类链段与卟啉大环活性基团的接触,显著改变了其电子状态。在TPP存在下薄膜的结构化导致低电压交流电导率增加,并记录到强烈的麦克斯韦-瓦格纳极化。在高电压极化时,也观察到TPP掺杂薄膜的电导率增加了一个数量级。在薄膜形成过程中引入TPP促进了单体单元中“头对头”型化学附着缺陷向表面的位移。这一过程伴随着薄膜表面粗糙度的显著增加,这通过压电力显微镜记录下来。后一种方法还揭示了在局部压电系数测量过程中出现的滞后现象。