Conformational Analysis of Conjugated Organic Materials: What Are My Heteroatoms Really Doing?

Organic semiconductor small molecules and polymers often incorporate heteroatoms into their chemical structures to affect the electronic properties of the material. A particular design philosophy has been to use these heteroatoms to influence torsional potentials, since the overlap of adjacent π-orbitals is most efficient in planar systems and is critical for charge delocalization in these systems. Since these design rules became popular, the messages from the earlier works have become lost in a sea of reports of "conformational locks", where the non-covalent interactions have relatively small contributions to planarizing torsional potentials. Greater influences can be found in the stabilization by extended conjugation, consideration of steric repulsion, and the interactions involving solubilizing chains and neighboring molecules or polymer chains in condensed phases.
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