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Polymerization-Enabled Excited-State Engineering for Organic Functional Materials
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DOI：10.1016/j.progpolymsci.2026.102123.png)
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Abstract
En 中文
Excited states govern fluorescence, phosphorescence, charge/energy transfer, and photosensitization in organic functional materials, yet their regulation has long relied on molecular design based on chemical composition and structure. Such approaches offer limited control over excited-state processes in condensed phases, where collective interactions and hierarchical organization play decisive roles. Recent advances further show that polymerization enables a new regime of excited-state engineering through hierarchical structural organization and collective electronic coupling beyond the reach of small molecules. In this review, we introduce polymerization-enabled excited-state engineering (PEESE) as a conceptual framework that integrates polymer chemistry, hierarchical structural design, and excited-state photophysics and photochemistry. First, we summarize the evolution of polymer backbone units from π-conjugated to nonconjugated heteroatom-rich structures, together with polymerization strategies that define hierarchical architectures governing excited-state behaviors. We then discuss three representative polymerization-induced or polymerization-enhanced processes for fluorescence, phosphorescence, and photosensitization, which are unified within the PEESE framework by hierarchical polymer structures spanning structural units, chain conformation, end groups, topology, and aggregation. We further provide theoretical and computational insights into how hierarchical polymer structures govern excited-state behaviors. By elevating excited states from molecular attributes to emergent properties of polymeric condensed matter, PEESE provides a unifying language for understanding and designing excited-state processes in polymers, with potential relevance to broader hierarchical systems. We hope this review will stimulate further research and collaboration across polymer chemistry, materials science, and photophysics and photochemistry to deepen mechanistic understanding, drive materials innovation, and advance PEESE toward practical photonic and photochemical applications.
Keywords:
Excited-state engineering
Polymerization
Organic functional materials
Hierarchical structure
Photophysics
Journal
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26.1
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1.4K
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3.0W
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