Department of Chemistry and Biochemistry, University of California─Santa Cruz, Santa Cruz, California95064, United States.
Biomolecular cryo-Electron Microscopy Facility, University of California─Santa Cruz, Santa Cruz, California95064, United States.
J Phys Chem Lett. 2022 Nov 10;13(44):10275-10281. doi: 10.1021/acs.jpclett.2c02466. Epub 2022 Oct 28.
Viscoelastic liquid coacervate phases that are highly enriched in nonconjugated polyelectrolytes are currently the subject of highly active research from biological and soft-materials perspectives. However, formation of a liquid, electronically active coacervate has proved highly elusive, since extended π-electron interactions strongly favor the solid state. Herein we show that a conjugated polyelectrolyte can be rationally designed to undergo aqueous liquid/liquid phase separation to form a liquid coacervate phase. This result is significant both because it adds to the fundamental understanding of liquid/liquid phase separation but also because it opens intriguing applications in light harvesting and beyond. We find that the semiconducting coacervate is intrinsically excitonically coupled, allowing for long-range exciton diffusion in a strongly correlated, fluctuating environment. The emergent excitonic states are comprised of both excimers and H-aggregates.
富含非共轭聚电解质的粘弹液凝聚相是目前生物和软物质领域非常活跃的研究课题。然而,由于扩展的π-电子相互作用强烈有利于固态,形成液体、电子活性凝聚相一直难以实现。在此,我们表明,可以合理设计共轭聚电解质以进行水相的液/液相分离,从而形成液体凝聚相。这一结果不仅因为它增加了对液/液相分离的基本理解,而且因为它在光收集和其他方面开辟了有趣的应用,所以具有重要意义。我们发现半导体凝聚相本质上是激子耦合的,允许在强关联、波动的环境中进行长程激子扩散。新兴的激子态由激基复合物和 H-聚集体组成。