For over forty years, conjugated polymers (CPs) have been a source of enormous fundamental breakthroughs, enabling foundational insight into the nature of π-bonding and electron pairing, the creation of novel optoelectronic functionalities, and the development of commercially relevant technologies. Despite the achievement of significant technological milestones, the complex structural and energetic heterogeneities that define these materials preclude bandgap control at low energies, tailored interactions with infrared (IR) light, the study of fundamental physical phenomena, and the design and realization of new device functionalities. To address these modern challenges, we developed precision synthetic methods that provide control of the frontier orbital energetics, coplanarity of the conjugated backbone, intermolecular interactions, and many chemical, electronic, and structural features that affect electronic coherence within these π-conjugated macromolecules, enabling unprecedented levels of bandgap control from 1 → 0.1 eV. The utility of these materials for understanding emergent light-matter interactions that enable the transduction of IR photons and the extension of CPs into high-performance IR optoelectronics will be discussed. We subsequently discovered that narrow bandgaps afforded through extended π-conjugation are intimately related to the coexistence of nearly degenerate electronic states. Through articulating novel mechanisms of spin alignment, topology control, and exchange, we have enabled the synthesis of neutral CPs with ground states that span the entire range from “conventional” closed-shell structures to biradicaloids with varying degrees of open-shell character, to diradicals in both singlet (S = 0) and triplet (S = 1) spin-states. These materials exhibit weaker intramolecular electron-electron pairing and stronger electronic correlations than their closed-shell counterparts, which imparts novel optical, transient, transport, thermal, spin, magnetic, quantum, and coherent phenomena not previously measured in soft-matter (polymer) systems. These novel attributes have enabled new optoelectronic and device functionalities that cannot be realized with current semiconductor technologies and provide a remarkable platform to study new phenomena at the interface of various fields such as chemistry, condensed matter physics, and quantum matter.