2,2'-bithiophene derivatives, 5-ammoniumethylsulfanyl-2,2'-bithiophene (AESBT) and 5,5'-bis(ammoniumethylsulfanyl)-2,2'-bithiophene (BAESBT), have been designed for their incorporation in organic-inorganic materials based on iodometalates. Three layered compounds, (BAESBT)PbI(4), (AESBT)(4)Pb(3)I(10), and (AESBT)(3)Bi(2)I(9), have been synthesized as crystals from slowly cooled aqueous solution containing metal halide and bithiophene derivative salts. When starting from the diammonium cation, (BAESBT)PbI(4) hybrid perovskite is obtained. (BAESBT)PbI(4) adopts a triclinic cell (P1) with the lattice parameters a = 8.4741(5) A, b = 8.9255(6) A, c = 16.876(1) A, alpha = 88.328(5) degrees, beta = 81.806(4) degrees, gamma = 88.864(5) degrees, Z = 2. In the structure, PbI(4)(2)(-) perovskite sheets and diammonium cation layers alternate along c. The incorporation of the corresponding monoammonium cation (AESBT) leads to a head to tail arrangement of the molecules in the (AESBT)(4)Pb(3)I(10) hybrid, precluding the formation of the perovskite layers. (AESBT)(4)Pb(3)I(10) is orthorhombic, Pna2(1), with a = 38.333(4) A, b = 22.239(3) A, c = 8.448(2) A, Z = 4. The structure consists of corrugated layers of Pb(3)I(10)(4)(-) separated by organic layers of monoammonium cations. A similar relative situation of molecules in organic layers is observed in (AESBT)(3)Bi(2)I(9), with the inorganic sheets being built up from Bi(2)I(9)(3)(-) entities. (AESBT)(3)Bi(2)I(9) crystallizes in an orthorhombic cell (P2(1)2(1)2(1)) with a = 8.4564(6) A, b = 21.368(2) A, c = 30.747(2) A, Z = 4. In the three compounds, the molecular packings appear different, underlining the interplay between both organic and inorganic components. New packings are stabilized, as illustrated by an original mixed kappa-alpha type arrangement of the bithiophene units in (AESBT)(3)Bi(2)I(9). Furthermore, molecular interactions, especially of S.S type, appear stronger in the hybrids based on the monoammonium cations. The electrical conductivity of a (BAESBT)PbI(4) single crystal has also been investigated, revealing a semiconductive behavior with a characteristic energy of E(g) = 2.535 eV.

The first hybrid perovskites incorporating alcohol-based bifunctional ammonium cations, (HO(CH(2))(2)NH(3))(2)PbX(4) (X = I, Br), have been prepared and characterized. (HO(CH(2))(2)NH(3))(2)PbI(4) adopts a monoclinic cell, a = 8.935(1) A, b= 9.056(2) A, c = 10.214(3) A, beta = 100.26(1) degrees , V = 813.3(3) A(3), P2(1)/a, and Z = 2, and (HO(CH(2))(2)NH(3))(2)PbBr(4) is orthorhombic, a = 8.4625(6) A, b = 8.647(1) A, c = 19.918(2) A, V = 1457.5(2) A(3), Pbcn, and Z = 4. In the layered structures, a unique hydrogen-bond network connects adjacent perovskite layers, owing to OH....X, NH(3)(+)....X, and intermolecular NH(3)(+)...OH interactions. Its impact on the bonding features of the inorganic framework and on the quite short interlayer distance, in the case of (HO(CH(2))(2)NH(3))(2)PbI(4), is shown. As a result, a significant red shift of the exciton peaks (lambda = 536 nm (X = I), lambda = 417 nm (X = Br)), compared to other PbX(4)(2)(-)-based perovskite hybrids, is observed, revealing a reduced band gap. A reversible structural transition occurs at T = 96 degrees C (X = I) and T = 125 degrees C (X = Br). An orthorhombic cell of the high-temperature phase of (HO(CH(2))(2)NH(3))(2)PbI(4) with a(HT) = 18.567(6) A, b(HT) = 13.833(6) A, c(HT) = 6.437(2) A, and V = 1653 A(3) is proposed from powder X-ray diffraction. A change in the hydrogen bonding occurs, with molecules standing up in the interlayer space and OH parts probably interacting together, leading to a more conventional situation for ammonium groups and a more distorted perovskite layer. This is in accordance with the blue shift of the exciton peak to lambda = 505 nm (X = I) or to lambda = 374 nm (X = Br) during the phase transition.

The reaction of cobalt, nickel, copper and cadmium chlorides and bromides with 5-methylfurfural thiosemicarbazone (M5FTSC) leads to the formation of two series of new complexes: [M(M5FTSC) 2 X 2 ], [M(M5FTSC)X 2 ]. They have been characterized by spectroscopic studies (infrared, 1 H NMR, and electronic spectra). The crystal structures of the free ligand M5FTSC and of the compound [CuCl 2 (M5FTSC)] have been determined by X-ray diffraction methods. For the Co(II), Ni(II) and Cu(II) complexes, the central atom is coordinated through the sulphur atom and the azomethine nitrogen atom whilst for the Cd(II) complexes, the coordination atoms are the sulphur and furanic oxygen atoms instead of the azomethine nitrogen.