Sosorev Andrey Yu, Ponomarev Igor I, Dominskiy Dmitry I, Lyssenko Konstantin A, Parashchuk Olga D, Trukhanov Vasily A, Konstantinov Vladislav G, Dubinets Nikita O, Paraschuk Dmitry Yu
Faculty of Physics, Lomonosov Moscow State University, Leninskie Gory 1/62, Moscow 119991, Russia.
Enikolopov Institute of Synthetic Polymeric Materials, Russian Academy of Science, Profsoyuznaya 70, Moscow 117393, Russia.
Phys Chem Chem Phys. 2023 Jul 26;25(29):19562-19575. doi: 10.1039/d3cp01582c.
Derivatives of naphthalene-diimide (NDI) are among the most studied and popular organic semiconductors showing n-type conductivity. However, the structure and optoelectronic properties of crystalline NDIs -functionalized with conjugated donors have not been investigated yet. In this study, a novel donor-acceptor compound NDI-Stb bearing one NDI core, as an acceptor, and two stilbene moieties covalently linked imide positions of NDI, as a donor, was synthesized. A combined experimental and theoretical approach was applied to study the structure and properties of NDI-Stb molecules and its crystals. We found and explained why optical absorption and high-frequency Raman spectra are inherited from those of donor and acceptor moieties, but photoluminescence is determined by the properties of the whole molecule. We resolved the structure of NDI-Stb single crystals and found that strong intermolecular interactions operate along two directions, for which NDI cores stack either on similar cores or on stilbene moieties. These interactions cause suppression of dynamic disorder indicated by a weak low-frequency Raman signal and solid-state luminescence enhancement. Ambipolar charge transport was predicted, and electron transport was experimentally observed in NDI-Stb polycrystalline thin films. The results obtained highlight the potential of using NDIs -functionalized with conjugated donor moieties in optoelectronic applications, and improve the understanding of structure-property relationships necessary for the rational design of novel donor-acceptor organic semiconductors.
萘二亚胺（NDI）衍生物是研究最多且最受欢迎的显示n型导电性的有机半导体之一。然而，用共轭供体功能化的结晶NDI的结构和光电性质尚未得到研究。在本研究中，合成了一种新型的供体-受体化合物NDI-Stb，它含有一个作为受体的NDI核以及两个作为供体的与NDI的酰亚胺位置共价连接的芪基部分。采用实验和理论相结合的方法来研究NDI-Stb分子及其晶体的结构和性质。我们发现并解释了为什么光吸收和高频拉曼光谱继承自供体和受体部分的光谱，但光致发光由整个分子的性质决定。我们解析了NDI-Stb单晶的结构，发现沿着两个方向存在强分子间相互作用，对于这两个方向，NDI核要么堆叠在相似的核上，要么堆叠在芪基部分上。这些相互作用导致低频拉曼信号减弱所表明的动态无序的抑制以及固态发光增强。预测了双极性电荷传输，并在NDI-Stb多晶薄膜中通过实验观察到了电子传输。所获得的结果突出了使用用共轭供体部分功能化的NDI在光电子应用中的潜力，并增进了对合理设计新型供体-受体有机半导体所需的结构-性质关系的理解。
