Structure and Optical Properties of Several Organic−Inorganic Hybrids Containing Corner-Sharing Chains of Bismuth Iodide Octahedra

Abstract

Two organic-inorganic bismuth iodides of the form (H3N-R-NH3)BiI5 are reported, each containing long and relatively flexible organic groups, R. The norganic framework in each case consists of distorted BiI6 octahedra sharing cis vertexes to form zigzag chains. Crystals of (H3NC18H24S2NH3)BiI5 were grown from a slowly cooled ethylene glycol/2-butanol solution containing bismuth(III) iodide and AETH.2HI, where AETH = 1,6-bis[5'-(2' '-aminoethyl)-2'-thienyl]hexane. The new compound, (H2AETH)BiI5, adopts an orthorhombic (Aba2) cell with the lattice parameters a = 20.427(3) A, b = 35.078(5) A, c = 8.559(1) A, and Z = 8. The structure consists of corrugated layers of BiI5(2-) chains, with Bi-I bond lengths ranging from 2.942(3) to 3.233(3) A, separated by layers of the organic (H2AETH)(2+) cations. Crystals of the analogous (H3NC12H24NH3)BiI5 compound were also prepared from a concentrated aqueous hydriodic acid solution containing bismuth(III) iodide and the 1,12-dodecanediamine (DDDA) salt, DDDA.2HI. (H2DDDA)BiI5 crystallizes in an orthorhombic (Ibam) cell with a = 17.226(2) A, b = 34.277(4) A, c = 8.654(1) A, and Z = 8. The Bi-I bonds range in length from 2.929(1) to 3.271(1) A. While the inorganic chain structure is nearly identical for the two title compounds, as well as for the previously reported (H3NC6H12NH3)BiI5 [i.e., (H2DAH)BiI5] structure, the packing of the chains is strongly influenced by the choice of organic cation. Optical absorption spectra for thermally ablated thin films of the three organic-inorganic hybrids containing BiI5(2-) chains are reported as a function of temperature (25-290 K). The dominant long-wavelength feature in each case is attributed to an exciton band, which is apparent at room temperature and, despite the similar inorganic chain structure, varies in position from 491 to 541 nm (at 25 K).

Lead‐Free Hybrid Perovskite Absorbers for Viable Application: Can We Eat the Cake and Have It too?

“…(H 3 NC 6 H 12 NH 3 )BiI 5 and (TMP)BiX 5 : 1,6‐hexane diammonium bismuth halide (H 3 NC 6 H 12 NH 3 )BiI 5 (HDABiI 5 ) showing 1D chains structure has early been reported by Mousdis et al196 and Mitzi et al,197 respectively ( Figure 18 a,b). Owning an optical bandgap of ≈2.0 eV, Fabian and Ardo198 first applied HDABiI 5 as a light absorber in PSCs.…”

Bismuth Iodide Hybrid Organic‐Inorganic Crystal Structures and Utilization in Formation of Textured BiI3 Film

“…[1,2] This is mainly due to the large number of screening electrons in bismuth, giving a large energy difference between the outermost s and p orbitals. The s-electrons are only loosely bound to the charged atom, which give the bismuth ion (Bi 3+ ) its characteristics as a polarizable ion causing the degree of distortion and aggregation of BiI 6 n-octahedra to vary extensively.…”

Synthesis, Crystal Structure and Infrared Characterization of Bis(4-dimethylamino-pyridinium) Tetrachlorocuprate

“…These weak interactions exercise important effects on the architecture and properties of many materials in various fields such as biology [4] [5] and crystal engineering [6] [7]. The control of these interactions will be important for the design of materials with specific types of properties such as conductivity or magnetic behavior [8]. Several works were focused on copper (II) halides to study the influence of the organic cation features on the packing interactions that govern the structural organization and consequently on the properties of this kind of complex [9] [10].…”