Influence of organic cation planarity on structural templating in hybrid metal-halides.

Controlling the connectivity and topology of solids is a versatile way to target desired physical properties. This is especially relevant in the realm of hybrid halide semiconductors, where the long-range connectivity of the inorganic substructural unit can lead to significant changes in optoelectronic properties such as photoluminescence, charge transport, and absorption. We present a new series of hybrid metal-halide semiconductors, (phenH)BiI·HO, (2,2-bpyH)BiI, (BrbpyH)BiI·HO, (phenH)PbI·2HO, and (2,2-bpyH)PbI where (phenH) = 1,10-phenanthroline-1,10-diium, (2,2-bpyH) = 2,2'-bipyridine-1,1'-diium and (BrbpyH) = 6,6'-dibromo-2,2'-bipyridium.

Hybrid Charge-Transfer Semiconductors: (CH)SbI, (CH)BiI, and Their Halide Congeners.

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, (CH)MX (M = Bi, Sb; X = Cl, Br, I), that are composed of edge-sharing MX chains separated in space by π-stacked tropylium (CH) cations; the inorganic chains resemble the connectivity of BiI. The Bi compounds have blue-shifted optical absorptions relative to the Sb compounds that span the visible and near-IR region.