Hybrid Organic Lead Iodides: Role of Organic Cation Structure in Obtaining 1D Chains of Face-Sharing Octahedra vs 2D Perovskites

((R(CH2)nNH3+ cations (R = aryl, substituted cyclohexyl; n = 1, 2) can form hybrid lead iodides that include both 2D layered perovskites of formula [R(CH2)nNH3]2PbI4 and 1D structures consisting of 1D wires of face-sharing PbI6 octahedra and having the formula [R(CH2)nNH3]PbI3 (face-sharing lead iodide chains, FSLICs). Using a series of such cations, we find that 1D FSLIC formation is favored when hydrogen bonding is possible between the ammonium moiety of one cation and a hydrogen-bond acceptor substituent of the same or another cation. A total of 16 new hybrid organic lead iodide crystal structures, 11 of which are FSLICs, are reported. The FSLIC structures can be further categorized according to the arrangement of neighboring wires. The optical properties of these materials are largely insensitive to the identity of the organic cations and to the resulting structural details. However, there is a correlation between the exciton energy and the pattern in which the wires are arranged relative to one another. Density functional theory calculations indicate that the dispersion at the top of the valence band varies depending on the relative wire arrangement. © 2022 American Chemical Society