Influence of π‑Iodide Intermolecular Interactions on Electronic Properties of Tin(IV) Iodide Semiconducting Complexes

Coordination compounds with a tin
center surrounded by both organic and inorganic ligands ([SnI4{(C6H5)3PO}2],
[SnI4{(C6H5)2SO}2], and [SnI4(C5H5NO)2]) acting as molecular semiconductors are in the spotlight of this
article. This is a new class of hybrid semiconducting materials where
optoelectronic properties of inorganic core (SnI4) were
tuned by organic ligands. The valence band is located at the inorganic
portion of the molecule while the conduction band is made of carbon-based
orbitals. This suggests the great importance of hydrogen bonds where
iodine atoms play the role of an acceptor. Weak intermolecular interactions
between iodine atoms and aromatic rings are essential in a band structure
formation. These materials form orange-red crystals soluble in most
of organic solvents. Their semiconducting properties are addressed
experimentally via photovoltage measurements, as well as theoretically,
using DFT and semiempirical approaches.