| The purpose of this work is to synthesize and characterize a family of organic-based tin(II) iodide layered perovskites—[H3N(CH 2)mNH3](CH3NH 3)n−1SnnI 3n+1 (n = 1–4, m = 4–6, 7, 8, 9, 12). The crystalline hybrid compounds were prepared by crystallization from acidic HI solutions (Method I) and by gel techniques (Method II). The crystal structures of the resulting products were characterized by single crystal X-ray diffraction and IR spectroscopy. Their electronic structure and chemical bonding were investigated by UV-VIS reflectance spectroscopy, 4-probe resistivity measurements, and electronic band structure calculations.; Normal flat single-layered perovskites with a variety of alkyldiamines—[H 3N(CH2)mNH3]SnI 4 (m = 4–6, 8, 9), were obtained from Method I, while those with longer hydrocarbon chains, e.g. [H3N(CH2)12NH 3]SnI4, were synthesized by Method II. The typical unit cell of these compounds consist of a 2-dimensional inorganic anion [SnI4 2−]—mono-layered perovskite sheets, and layers of [H 3N(CH2)mNH3] 2+ cations packed between the inorganic sheets. An unexpected corrugated anion sheet, [SnI4]2−, was also observed, for the first time, in α-[H3N(CH2)SNH3]SnI 4.; The multi-layered perovskite hybrid compounds—the double-layered [H3N(CH2)SNH3](CH3NH3)SnI 7, the triple-layered perovskites [H3N(CH 2)4NH3](CH3NH3)2Sn 3I10, and [H3N(CH2)6NH 3](CH3NH3)2Sn3I10, and a quadruple-layered [H3N(CH2)SNH3](CH 3NH3)3Sn4I13 were obtained in polycrystalline and single crystalline forms. Single crystal X-ray diffraction, electronic band structure calculations, and electronic resistivity measurements were performed on representative members of the family of hybrid perovskites.; Attempts to introduce nonprimary amines into the layered perovskite structures resulted in the preparation of 2,2′-biimidazolium tin iodide—[NH(CH)2NHC]2SnI4 and morpholinium tin iodide[O(CH2)2NH2(CH2) 2]2SnI4. These are the first reports of nonprimary amine-based layered perovskite structures. Their crystal structures reveal significant deviations from typical layered perovskite structures, characterized by severely distorted SnI6 octahedral units. Electronic band structure calculations, using the tight-binding approach, reveal significant interplay of the stereoactivity of the Sn(II) lone-pairs with the onset of hypervalent secondary bonding in morpholinium tin iodide. Thus, the seemingly layered perovskite structure of morpholinium tin iodide exhibits a one-dimensional bonding character.; Two unprecedented three-dimensional (3-D) defect perovskite compounds, [H3N(CH2)7NH3]2Sn 3I10 and [H3N(CH2)7NH 3]8(H3NCH3)2Sn(IV)Sn(II) 12I46 were prepared. Their novel 3-D structures can be derived from the ordered arrangement of vacancies on the metal and anion s... |
