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Abstract: Reaction of chlorotrisulfidomolybdate [PPh4][MoClS3] (1) with one equivalent of tridentate ligand PyCH2NHC2H4SNa (PyNSNa) in THF generated both a mononuclear and a dinuclear complexes, [PPh4][(PyNS)MoO(η 2-S2)2] (2) and [PPh4][(PyNS)Mo(O)(μ-S)2Mo(S)(η 2-S2)]·0.5MeCN (3·0.5MeCN). These two complexes were separated mechanically and fully characterized using IR, UV/Vis spectra, 1H NMR spectra and X-ray single crystal diffraction analysis. In both complexes, one terminal sulfido ligand was substituted by one oxo group. In complex 3, two types of intermolecular hydrogen bonding in its solid state led to a 1-D structure in which each unit was a dimmer formed via hydrogen bonding. [Copyright &y& Elsevier]

Two inorganic–organic hybrid compounds [(C 7 H 18 N 2 ) 6 Pb 7 I 26 ] ( 1 ) and [(C 7 H 18 N 2 )Pb 2 I 6 ] ( 2 ) have been synthesized by reactions of 2-(2-aminoethyl)-1-methylpyrrolidine and lead iodide with 1: 1 and 1: 2 M ratios in concentrated HI aqueous. The single-crystal X-ray diffraction revealed that the inorganic component in compound 1 can be viewed as a wave-like 2D sheet built up from alternatively perovskite and non-perovskite structure types connected with corner-, edge- sharing octahedral [PbI 6 ]; and that in complex 2 is a zigzag chain constructed with edge- sharing octahedral [PbI 6 ]. In addition, both complexes showed fluorescent properties with complex 1 emitted green light at 545 nm and complex 2 emitted blue light at 467 nm. [ABSTRACT FROM AUTHOR]

The reaction of manganese(II) halide MnCl 2 ·4H 2 O and tris(2-aminoethyl)amine N(CH 2 CH 2 NH 2 ) 3 in the concentrated acid HCl at 65 °C resulted in the formation of an inorganic–organic hybrid complex: [(C 6 H 22 N 4 ) 2 (H 3 O)(MnCl 6 )(MnCl 5 )(Cl) 2 ]·3H 2 O ( 1 ) and a known byproduct [(C 6 H 22 N 4 )Cl 4 ]·H 2 O. The analogue reactions between MnBr 2 ·4H 2 O and N(CH 2 CH 2 NH 2 ) 3 in HBr acid gave a pure complex [(C 6 H 22 N 4 ) 2 Br 5 ](MnBr 5 ) ( 2 ). Crystal structures revealed that Mn centers in 1 adopted trigonal bipyramidal and octahedral two geometries, while in 2 showed only trigonal bipyramidal geometry. Luminescent investigation exhibited complex 1 gave pink luminescence and complex 2 emitted yellow light in solid states, which were both directly originated from the coordinated geometries of Mn 2+ ion. [ABSTRACT FROM AUTHOR]

A discrete organic-inorganic hybrid compound [(3.2.1-dabco) 2 PbBr 6 exhibited a reversible phase transition which was originated from the order to disorder of spherical [3.2.1-dabco]2+ cation at RTP and HTP. • A spherical molecule 1, 5-diazabicyclo[3,2,1]octane was chose to react with PbBr 2 to give an organic-inorganic compound. • The obtained hybrid compound showed a reversible phase transition. • The variable temperature X-ray single crystal diffraction revealed the phase transition was derived from the order and disorder of spherical molecule at room temperature and high temperature. Organic-inorganic hybrid materials were attracted most interests due to their potential applications in phase transition and photoelectric fields. Within this context, a spherical molecule 1, 5-diazabicyclo[3,2,1]octane (3,2,1-dabco) was used to react with PbBr 2 in concentrated HBr acid and led to a discrete organic inorganic hybrid compound [(3,2,1-dabco) 2 PbBr 6 (1). Thermodynamic DSC analyses and dielectric measurement of 1 showed an apparently reversible phase transition at about 427 K. The variable temperature X-ray single crystal diffraction demonstrated compound 1 underwent an order-disorder transition from orthorhombic to cubic systems at room and high temperatures. [ABSTRACT FROM AUTHOR]

Abstract Due to its unique optical properties, two-dimensional (2D) organic-inorganic hybrid perovskite attracts wide attention. In this paper, series of 2D perovskites with the formula [(4-FBA) 2 (MA) n-1 Pb n I 3n + 1 ] (4-FBA = 4-FC 6 H 4 CH 2 NH 3 , MA = CH 3 NH 3 , n = 1, 2, 3, n represents the number of 2D perovskite inorganic layers) were obtained by controlling the starting material ratios among 4-fluorobenzylamine, methylammonium iodide and lead iodide. The multilayered perovskite structures were formed by slicing the 3D [MAPbI 3 ] with 4-fluorobenzylamine along the specific crystallographic plane. According to the UV−vis absorption, the bandgaps of the multilayered compounds decreased with the increase of inorganic perovskite layers (E g = 2.23 eV for n = 1; E g = 2.01 eV for n = 2 and E g = 1.78 eV for n = 3), thus leading to their potential application in solar cell. Graphical abstract Reactions of 4-fluorobenzylamine, methylammonium iodide and lead iodide with specific molar ratio in concentrated HI/H 3 PO 2 aqueous led to series of 2D multilayer lead iodide perovskites [(FC 6 H 4 CH 2 NH 3) 2 (CH 3 NH 3) n-1 Pb n I 3n + 1 ] (n = 1, 2, 3) with narrow bandgaps from E g = 2.23 eV (n = 1) to 1.78 eV (n = 3). Unlabelled Image Highlights • Series of 2D perovskites were obtained by reactions of 4-fluorobenzylamine, methylammonium iodide and PbI 2. • The number of layers of 2D perovskite can be adjusted by the reaction ratio. • The bandgaps of the multilayered compounds decreased with the increase of inorganic perovskite layers. [ABSTRACT FROM AUTHOR]

Abstract: Two Hg(II) complexes [HgL′(ClO4)2] (1) and [HgL(ClO4)]ClO4 (2) derived from the macrocyclic ligands, 4-(pyridin-2-ylmethyl)-1,7-dithia-4,10-diazacyclododecane (L′) and 7-(pyridin-2-ylmethyl)-1,4,10-trithia-7,13-diazacyclopentadecane (L), have been crystallographically characterised. Ligand L and its Hg(II) complex were isolated unexpectedly, and a possible formation pathway of the ligand is proposed. By including weakly bound O atoms from the perchlorate ions, the Hg atoms in both complexes are seven-coordinate and possess capped trigonal prismatic geometries. These uncommon structures for Hg(II) complexes were achieved mainly by the relatively large size of the metal ion and the steric effect from the macrocycles. In both complexes, strong hydrogen bonding between the amine hydrogen atom and a perchlorate ion was observed. For complex 1, the interaction is N(3)–H(15)···O(8) at 2.08(12)Å where O(8) is of the same anion as one of the coordinated O atoms; in complex 2, a similar hydrogen bond, N(7)–H(7)···O(32), with a distance of 2.25Å, is formed to the coordinated anion, but the second anion remains discrete. [ABSTRACT FROM AUTHOR]