Department of Chemistry, Lomonosov Moscow State University, 119991 Moscow, Russia.
Department of Materials Science, Lomonosov Moscow State University, 119991 Moscow, Russia.
Molecules. 2021 Sep 21;26(18):5712. doi: 10.3390/molecules26185712.
Despite remarkable progress in photoconversion efficiency, the toxicity of lead-based hybrid perovskites remains an important issue hindering their applications in consumer optoelectronic devices, such as solar cells, LED displays, and photodetectors. For that reason, lead-free metal halide complexes have attracted great attention as alternative optoelectronic materials. In this work, we demonstrate that reactions of two aromatic diamines with iodine in hydroiodic acid produced phenylenediammonium (PDA) and N,N-dimethyl-phenylenediammonium (DMPDA) triiodides, PDA(I)⋅2HO and DMPDA(I)I, respectively. If the source of bismuth was added, they were converted into previously reported PDA(BiI)⋅I and new (DMPDA)(BiI)(I)⋅2HO, having band gaps of 1.45 and 1.7 eV, respectively, which are in the optimal range for efficient solar light absorbers. All four compounds presented organic-inorganic hybrids, whose supramolecular structures were based on a variety of intermolecular forces, including (N)H⋅⋅⋅I and (N)H⋅⋅⋅O hydrogen bonds as well as I⋅⋅⋅I secondary and weak interactions. Details of their molecular and supramolecular structures are discussed based on single-crystal X-ray diffraction data, thermal analysis, and Raman and optical spectroscopy.
尽管光转换效率取得了显著进展，但基于铅的混合钙钛矿的毒性仍是阻碍其在太阳能电池、LED 显示器和光电探测器等消费型光电器件中应用的一个重要问题。出于这个原因，无铅金属卤化物配合物作为替代光电材料引起了极大关注。在这项工作中，我们证明了两种芳族二胺与氢碘酸中的碘反应，分别生成苯二铵（PDA）和 N,N-二甲基苯二铵（DMPDA）三碘化氢，即 PDA(I)⋅2HO 和 DMPDA(I)I。如果加入铋的来源，它们会转化为之前报道的 PDA(BiI)⋅I 和新的(DMPDA)(BiI)(I)⋅2HO，其带隙分别为 1.45 和 1.7 eV，分别在高效太阳能吸收器的最佳范围内。这四种化合物均为有机-无机杂化材料，其超分子结构基于多种分子间力，包括（N）H⋅⋅⋅I 和（N）H⋅⋅⋅O 氢键以及 I⋅⋅⋅I 次级和弱相互作用。基于单晶 X 射线衍射数据、热分析、拉曼和光谱学对其分子和超分子结构进行了详细讨论。
