Hybrid Charge-Transfer Semiconductors: (C7H7)SbI4, (C7H7)BiI4, and Their Halide Congeners

• DOI: 10.1021/acs.inorgchem.9b00170
• Publication Date: 2019-03-22T13:34:03Z
• Authors: Iain W. H. Oswald; Eve M. Mozur; Ian P. Moseley; Hyochul Ahn; James R. Neilson
• Keywords: Metal halides

Hybrid metal halides yield highly desirable optoelectronic properties and offer significant opportunity due to their solution processability. This contribution reports a new series of hybrid semiconductors, (C7H7)MX4 (M = Bi3+, Sb3+; X Cl-, Br-, I-), that are composed edge-sharing MX6 chains separated in space by π-stacked tropylium (C7H7+) cations; the inorganic resemble connectivity BiI3. The Bi3+ compounds have blue-shifted optical absorptions relative Sb3+ span visible near-IR region. Consistent with observations, DFT calculations reveal conduction band is cation valence primarily chain: charge-transfer semiconductor. gaps for both decrease systematically as function increasing halide size. These rare example semiconductors also exhibit efficient crystal packing organic cations, thus providing an study how structural affects properties.