Molecular and Supramolecular Structures of Triiodides and Polyiodobismuthates of Phenylenediammonium and Its N,N-dimethyl Derivative

• Published in: Molecules (Basel, Switzerland) Vol. 26; no. 18; p. 5712
• Main Authors: Shestimerova, Tatiana A., Golubev, Nikita A., Bykov, Mikhail A., Mironov, Andrei V., Fateev, Sergey A., Tarasov, Alexey B., Turkevych, Ivan, Wei, Zheng, Dikarev, Evgeny V., Shevelkov, Andrei V.
• Format: Journal Article
• Language: English
• Published: Basel MDPI AG 21.09.2021; MDPI
• Subjects: Asymmetry; Bismuth; Bonding strength; Chemical bonds; Crystal structure; Diamines; hybrid organic–inorganic compounds; Hybrids; Hydrogen bonding; Hydrogen bonds; Intermolecular forces; Iodine; Lead free; Light emitting diodes; Metal halides; molecular structure; Optical properties; Optoelectronic devices; Perovskites; phenylenediammonium; Quantum efficiency; Single crystals; Solar cells; Spectroscopy; supramolecular ensemble; Thermal analysis; Toxicity; triiodides; X-ray diffraction
• ISSN: 1420-3049; 1420-3049
• 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(I3)2⋅2H2O and DMPDA(I3)I, respectively. If the source of bismuth was added, they were converted into previously reported PDA(BiI4)2⋅I2 and new (DMPDA)2(BiI6)(I3)⋅2H2O, 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.