Hybrid Inorganic-Organic Materials with an Optoelectronically Active Aromatic Cation: (C₇H₇)₂SnI₆ and C₇H₇PbI₃

Journal Article · Thu Jun 04 00:00:00 EDT 2015 · Inorg. Chem.

DOI:https://doi.org/10.1021/ic5025795· OSTI ID:1168494

Maughan, Annalise E.; Kurzman, Joshua A.; Neilson, James R. ^[1]

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1. CSU

Inorganic materials with organic constituents—hybrid materials—have shown incredible promise as chemically tunable functional materials with interesting optical and electronic properties. Here, the preparation and structure are reported of two hybrid materials containing the optoelectronically active tropylium ion within tin- and lead-iodide inorganic frameworks with distinct topologies. The crystal structures of tropylium tin iodide, (C₇H₇)₂SnI₆, and tropylium lead iodide, C₇H₇PbI₃, were solved using high-resolution synchrotron powder X-ray diffraction informed by X-ray pair distribution function data and high-resolution time-of-flight neutron diffraction. Tropylium tin iodide contains isolated tin(IV)-iodide octahedra and crystallizes as a deep black solid, while tropylium lead iodide presents one-dimensional chains of face-sharing lead(II)-iodide octahedra and crystallizes as a bright red-orange powder. Experimental diffuse reflectance spectra are in good agreement with density functional calculations of the electronic structure. Calculations of the band decomposed charge densities suggest that the deep black color of tropylium tin iodide is attributed to iodide ligand to tin metal charge transfer, while the bright red-orange color of tropylium lead iodide arises from charge transfer between iodine and tropylium states. Understanding the origins of the observed optoelectronic properties of these two compounds, with respect to their distinct topologies and organic–inorganic interactions, provides insight into the design of tropylium-containing compounds for potential optical and electronic applications.

• Research Organization: Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
• Sponsoring Organization: NSFUNIVERSITY
• OSTI ID: 1168494
• Journal Information: Inorg. Chem., Vol. 54, Issue (1) ; 01, 2015
• Country of Publication: United States
• Language: ENGLISH