Molecular and Supramolecular Structures of Triiodides and Polyiodobismuthates of Phenylenediammonium and Its N,N-dimethyl Derivative |
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| Authors: | Tatiana A Shestimerova Nikita A Golubev Mikhail A Bykov Andrei V Mironov Sergey A Fateev Alexey B Tarasov Ivan Turkevych Zheng Wei Evgeny V Dikarev Andrei V Shevelkov |
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| Institution: | 1.Department of Chemistry, Lomonosov Moscow State University, 119991 Moscow, Russia; (T.A.S.); (N.A.G.); (M.A.B.); (A.V.M.); (A.B.T.);2.Department of Materials Science, Lomonosov Moscow State University, 119991 Moscow, Russia;3.Sensing System Research Center, National Institute of Advanced Industrial Science and Technology, Tsukuba 305-8565, Japan;4.Department of Chemistry, University at Albany, SUNY, Albany, NY 12222, USA; (Z.W.); (E.V.D.) |
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| Abstract: | 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. |
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| Keywords: | triiodides hybrid organic– inorganic compounds phenylenediammonium bismuth supramolecular ensemble molecular structure intermolecular interactions |
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