MS16-P03 Perovskite-type hybrid materials with lead halide complexes and piperidine methyl derivatives: Design, synthesis and structural analysis Pawel Socha (Department of Chemistry, University of Warsaw, Warsaw, Poland) Lukasz Dobrzycki (Department of Chemistry, University of Warsaw, Warsaw, Poland) Michal K. Cyranski (Department of Chemistry, University of Warsaw, Warsaw, Poland)email:
Perovskite-type halide hybrid salts are intriguing materials. Depending on the size and shape of an organic cation it is possible to obtain 0-D, 1-D, 2-D or
3-D architecture of polymerized inorganic complexes in the crystal structure. Physicochemical properties of these materials strictly depend on this architecture, kind of metal cation and halide anion, what gives many possibilities of modification depending on creators preferences. Therefore, hybrid salts are known as semiconductors, magnetics or solar cell components. [1] [2]
The aim of this project is design, synthesis and structural analysis of new organometallic systems of lead halides – piperidine (and its derivatives). Based on the received results, it is available to propose the rules governing the crystal architecture of the hybrid salts.
Piperidine is a six-membered heterocyclic aliphatic amine, which may be relatively easily modified by substitution e.g. by methyl group in various position(s) in respect to the nitrogen atom. Size of the organic cation should affect crystal structure, because it can fill more space in the unit cell. Additionally, covering of amine group should have influence on structure, because of reduce accessibility atoms to create hydrogen bonds between organic and inorganic part.
Lead halide was chosen as an inorganic part of hybrid material. It is well known that lead halide creates octahedral complex of PbX6-4, hence it was expected to receive various motifs of polymerized inorganic complexes like 1-D chains, 2-D layers or 3-D motifs. [1][2][3] Chlorides and bromides was used independently as halides.
During the studies, 9 crystals were obtained. All structures were determined by single crystal x-ray diffraction and additionally characterized by Raman spectroscopy. For systems containing lead bromide, 5 of them exhibit 1-D inorganic chain structure. Structural analysis showed that, few of them are isostructural despite the different position of the methyl group. Moreover, one of them form uncommon 3-D inorganic structure (Fig. 1), what is exception in the examinated series of systems with piperidine derivatives and lead bromide. In contrast to the previous systems, 3 obtained crystals with lead chloride represent only 2-D architecture, which draws attention to the influence of the size of used halogen anion.

[1] Liu, M., Johnston, M. B. & Snaith, H. J. (2013). Nature, 501, , 395–398

[2] Ye, H.-Y., Liao, W.-Q., Hu, C.-L., Zhang, Y., You, Y.-M., Mao, J.-G., Li, P.-F. & Xiong, R.-G. (2016). Adv. Mater., 28, 2579–2586

[3] Dobrzycki, L. & Wozniak, K. (2009). Journal of Molecular Structure 921, 18–33
Keywords: Hybrid materials, Perovskite-type halides, Crystal engineering