Effects of molecular architecture on morphology and photophysics in conjugated polymers: from single molecules to bulk

Conjugated polymers (CPs) possess a wide range of desirable properties, including accessible energetic bandgaps, synthetic versatility, and mechanical flexibility, which make them attractive for flexible and wearable optoelectronic devices. An accurate and comprehensive understanding about the morphology–photophysics relations in CPs lays the groundwork for their development in these applications. However, due to the complex roles of chemical structure, side-chains, backbone, and intramolecular interactions, CPs can exhibit heterogeneity in both their morphology and optoelectronic properties even at the single chain level. This molecular level heterogeneity together with complicated intermolecular interactions found in bulk CP materials severely obscures the deterministic information about the morphology and photophysics at different hierarchy levels. To counter this complexity and offer a clearer picture for the properties of CP materials, we highlight the approach of probing material systems with specific structural features via single molecule/aggregate spectroscopy (SMS). This review article covers recent advances achieved through such an approach regarding the important morphological and photophysical properties of CPs. After a brief review of the typical characteristics of CPs, we present detailed discussions of structurally well-defined model systems of CPs, from manipulated backbones and side-chains, up to nano-aggregates, studied with SMS to offer deterministic relations between morphology and photophysics from single chains building up to bulk states.