Conjugated polyelectrolyte-based ternary exciton funnels <i>via</i> liposome scaffolds

Palmer, J. S.; Segura, Carmen; Matsushima, Levi N.; Abrams, Benjamin; Lee, Hsiau‐Wei; Ayzner, Alexander L.

doi:10.1039/d1me00139f

Cited by 3 publications

(3 citation statements)

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“…Conjugated polyelectrolytes are a material platform that can support long-range energy transfer and enhanced charge mobility when paired with counterions that induce extended π-delocalization as a result of noncovalent interactions. ,− Electrolytes have been used to process films with ordered microstructures and photovoltaic devices with improved charge transport. ,− Relatively recently, oppositely charged conjugated polyelectrolytes have been paired in solutions to form what are known as conjugated polyelectrolyte complexes (CPECs) and have been investigated for their light-harvesting potential in solutions and other complex environments. ,,− For example, a rudimentary light-harvesting complex has been demonstrated using a polyelectrolyte complex that associates with a membrane and facilitates energy transfer to an acceptor located at the membrane’s interior . Photoinduced charge transfer has also been observed between polyelectrolytes and electrolytic small-molecule acceptors. ,, Charge-transfer behavior has been shown to be sensitive to specifics of polyelectrolyte interactions, , and long-lived charge separation with potential for photoredox chemistry has been demonstrated …”

Section: Introductionmentioning

confidence: 99%

“…6,20,24−29 For example, a rudimentary light-harvesting complex has been demonstrated using a polyelectrolyte complex that associates with a membrane and facilitates energy transfer to an acceptor located at the membrane's interior. 28 Photoinduced charge transfer has also been observed between polyelectrolytes and electrolytic smallmolecule acceptors. 6,24,25 Charge-transfer behavior has been shown to be sensitive to specifics of polyelectrolyte interactions, 24,25 and long-lived charge separation with potential for photoredox chemistry has been demonstrated.…”

Section: Introductionmentioning

confidence: 99%

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Electron Transfer in Conjugated Polymer Electrolyte Complexes: Impact of Donor–Acceptor Interactions on Microstructure, Charge Separation, and Charge Recombination

Clark-Winters

Bragg

2022

J. Phys. Chem. C

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Conjugated polyelectrolyte complexes (CPECs) are an artificial light-harvesting platform formed by pairing oppositely charged conjugated polyelectrolytes in solution. We demonstrate that selective pairing of poly[3-(potassium-4-alkanoate)thiophene-2,5-diyl] (PTAK) of various regioregularity and side-chain lengths with either methyl viologen or an electrolytic naphthalene diimide electron acceptor supports different PTAK microstructures based on specific donor−acceptor stacking relationships. Alteration in microstructure is signaled by distinct signatures of excitonic coupling in steady-state absorption spectra. More ordered PTAK microstructures are obtained in CPECs formed with regioregular PTAK and when the distance between charged groups on the acceptor and PTAK matches. Photoinduced dynamics in these CPECs are characterized by sub-100-fs PTAK-to-acceptor electron transfer with polaron-pair generation in PTAK quenched in higher-order complexes. Rates of subsequent multiphasic charge recombination on picosecond-to-nanosecond timescales are determined by structural characteristics associated with specific donor− acceptor pairings and acceptor-dependent driving force for recombination, with longer-lived charge pairs observed in highly ordered CPEC microstructures. CPECs also demonstrate structure-dependent sensitivity to excitation energy and intensity; excitation energies significantly exceeding PTAK band energy increase exciton delocalization, particularly in complexes with higher structural order. The structure dependence of charge-transfer behaviors in CPECs provides insights for inducing long-range charge separation in related materials for light-harvesting applications.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Electron Transfer in Conjugated Polymer Electrolyte Complexes: Impact of Donor–Acceptor Interactions on Microstructure, Charge Separation, and Charge Recombination

Clark-Winters

Bragg

2022

J. Phys. Chem. C

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“…Solar-energy conversion via photosynthesis relies on noncovalent interactions between light-harvesting antennae pigments and neighboring chromophores to yield efficient energy and electron transfer. − Photosynthetic mimicry (or artificial photosynthesis) continues to inspire investigations of how through-space interactions may be controlled or tuned to support these behaviors. − Supramolecular assemblies and complexes of energy or electron donor and acceptor pigments hold promise for facilitating long-range energy or electron transfer , that is needed for harvesting photon energy in order to drive redox chemistry at a sparse collection of reaction centers. − Subtle changes to structures of constituent molecules may be used to alter the nature of molecular interactions in assemblies or complexes, or fine-tune their transport behaviors for photogenerated excitations (excitons) and charges. In this paper, we report on structure- and energy-dependent photoinduced electron transfer in conjugated polyelectrolyte complexes (CPECs), ,− which are composed of oppositely charged, visible-light-responsive polymers.…”

Section: Introductionmentioning

confidence: 99%

Energy-Dependent Charge Separation in Conjugated Polymer Electrolyte Complexes

Clark-Winters

Bragg

2023

J. Phys. Chem. C

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Supramolecular complexes have great potential as lightharvesting materials, as intermolecular structural organization can be manipulated through steric or electrostatic interactions to impact electronic coupling between energy and charge donors and acceptors. Here, we examine the relative rates and efficiencies of charge transfer in conjugated polymer electrolyte complexes (CPECs) based on a polythiophene electron donor (PTAK) and polyfluorene electron acceptor (PFPI). These CPECs are characterized by ordered polymer microstructures, as evident from spectral signatures of strong excitonic coupling within the PTAK component from steady-state UV−vis absorption spectra. We find that PTAK polarons are generated within tens of picoseconds through a combination of prompt and delayed charge separation following direct photoexcitation or energy transfer from PFPI. Further, we find that decreasing the length of charged PTAK side chains or increasing excitation energy increases the driving force for electron transfer to increase charge separation rates and yields for polarons, with the greatest relative yields observed at excitation energies that initiate PFPI-to-PTAK energy transfer. Charge separation between components can be rationalized from a canonical Marcus picture, whereby excess vibrational energy effectively lowers the barrier for PTAK-to-PFPI charge separation. This contrasts with the recently reported ultrafast (<100 fs) charge separation in small-molecule/polythiophene electrolyte complexes that is attributed to strong orbital mixing that gives rise to charge generation via CT exciton states. These results provide insights into conditions for realizing charge separation in concert with energy transfer in CPECs as light-harvesting materials.

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The Materials and Application of Artificial Light Harvesting System Based on Supramolecular Self‐assembly

et al. 2023

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Supramolecular self‐assembly is the process of forming aggregates with a certain microscopic arrangement by using intermolecular interactions to join. Due to the dynamic controllability of supramolecular systems, many supramolecular systems with different functions can be precisely constructed through the design and modification of molecules. The world is now facing a crisis caused by energy problems, and the use of solar energy, especially how to achieve efficient collection of light energy like photosynthesis in nature, has become a challenge. Scientists have come up with the idea of using the tunable nature of supramolecular structure and function to construct artificial light harvesting systems, and have developed a series of ALHS based on this. Currently, ALHS have been applied to imaging, sensors, photoelectric conversion and molecular recognition, laying the foundation for the development and efficient use of light energy. This paper will review the mechanism and method of constructing ALHS based on Supramolecular Self‐assembly, the current hot materials for constructing ALHS and their characteristics, as well as the prospects and applications.

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Conjugated polyelectrolyte-based ternary exciton funnels via liposome scaffolds

Abstract: There is great interest in developing inexpensive, molecular light-harvesting systems capable of efficiently converting photon energy to chemical potential energy. It is highly desirable to do so using self-assembly and...

Cited by 3 publications

References 36 publications

Electron Transfer in Conjugated Polymer Electrolyte Complexes: Impact of Donor–Acceptor Interactions on Microstructure, Charge Separation, and Charge Recombination

Electron Transfer in Conjugated Polymer Electrolyte Complexes: Impact of Donor–Acceptor Interactions on Microstructure, Charge Separation, and Charge Recombination

Energy-Dependent Charge Separation in Conjugated Polymer Electrolyte Complexes

The Materials and Application of Artificial Light Harvesting System Based on Supramolecular Self‐assembly

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