Institute of Chemistry, University of Silesia, 9 Szkolna Str., 40-006 Katowice, Poland.
Centre of Polymer and Carbon Materials, Polish Academy of Sciences, 34 M. Curie-Sklodowska Str., 41-819 Zabrze, Poland.
Int J Mol Sci. 2022 Jul 24;23(15):8160. doi: 10.3390/ijms23158160.
A new series of thiophene-based azomethines differing in the core structure was synthesized. The effect of the central core structure in azomethines on the thermal, optical and electrochemical properties was investigated. The obtained compounds exhibited the ability to form a stable amorphous phase with a high glass transition temperature above 100 °C. They were electrochemically active and undergo oxidation and reduction processes. The highest occupied (HOMO) and the lowest unoccupied molecular (LUMO) orbitals were in the range of -3.86--3.60 eV and -5.46--5.17 eV, respectively, resulting in a very low energy band gap below 1.7 eV. Optical investigations were performed in the solvents with various polarity and in the solid state as a thin film deposited on a glass substrate. The synthesized imines absorbed radiation from 350 to 600 nm, depending on its structure and showed weak emission with a photoluminescence quantum yield below 2.5%. The photophysical investigations were supported by theoretical calculations using the density functional theory. The synthesized imines doped with lithium bis-(trifluoromethanesulfonyl)imide were examined as hole transporting materials (HTM) in hybrid inorganic-organic perovskite solar cells. It was found that both a volume of lithium salt and core imine structure significantly impact device performance. The best power conversion efficiency (PCE), being about 35-63% higher compared to other devices, exhibited cells based on the imine containing a core tiphenylamine unit.
合成了一系列在核心结构上有所不同的基于噻吩的偶氮化合物。研究了偶氮化合物中中心核结构对热、光和电化学性能的影响。所得化合物具有形成稳定非晶相的能力,玻璃化转变温度高于 100°C。它们具有电化学活性,并经历氧化和还原过程。最高占据(HOMO)和最低未占据分子(LUMO)轨道分别在-3.86--3.60 eV 和-5.46--5.17 eV 的范围内,导致能隙非常低,低于 1.7 eV。在具有不同极性的溶剂中和作为沉积在玻璃基底上的薄膜的固态中进行了光学研究。合成的亚胺在 350 至 600nm 之间吸收辐射,这取决于其结构,并显示出光致发光量子产率低于 2.5%的弱发射。通过使用密度泛函理论的理论计算来支持光物理研究。用双(三氟甲烷磺酰基)亚胺锂掺杂合成的亚胺,作为混合无机-有机钙钛矿太阳能电池中的空穴传输材料(HTM)进行了研究。结果发现,锂盐的体积和核亚胺结构都显著影响器件性能。与其他器件相比,基于含有三苯胺核单元的亚胺的电池的功率转换效率(PCE)提高了约 35-63%,表现最佳。