Crystal structure, vibrational and optical properties of a new self-organized material containing iodide anions of bismuth(III), [C6H4(NH3)2]2Bi2I10•4H2O

Bismuth-iodide type zero-dimensional (0-D) organic/inorganic hybrid compound [C6H4(NH3)212 Bi2I10 center dot 4H(2)O was synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in the monoclinic space group P2(1)/n, with a=11.483(5), b=12.896(5), c=14.974(5) angstrom, beta= 112.437 degrees(5) and Z = 4; and consists of a p-phenylenediammonium dications, water molecules of crystallization in addition to the anion, which is built up of edge-sharing bioctahedra. The crystal packing is governed by I center dot center dot center dot I electrostatic interactions and ionic N-H center dot center dot center dot I hydrogen bonds forming a self-assembled multiple zero-dimensional structure. Raman and infrared spectra of the title compound were recorded in the 0-170 and 400-4000 cm(-1) frequency regions, respectively. An assignment of the observed vibration modes is reported. Optical transmission measurements on thin films of [C6H4(NH3)(2)](2)Bi2I10 center dot 4H(2)O revealed two absorption bands at 2.84 and 2.4 eV. Photoluminescence measurements showed a strong emission line at 2.13 eV associated with radiative recombinations of excitons confined within the bioctahedra Bizlio (C) 2011 Elsevier B.V. All rights reserved.