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Fine-tuning the microstructure and photophysical characteristics of fluorescent conjugated copolymers using photoalignment and liquid-crystal ordering

Abstract:
Replicating the microstructural basis and the near 100% excitation energy transfer efficiency in naturally occurring light-harvesting complexes (LHCs) remains challenging in synthetic energy-harvesting devices. Biological photosynthesis regulates active ensembles of light-absorbing and funneling chlorophylls in proteins in response to fluctuating sunlight. Here, use of long-range liquid crystal (LC) ordering to tailor chain orientation and packing structure in liquid crystalline conjugated polymer (LCCP) layers for bio-mimicry of certain structural basis and light-harvesting properties of LHCs is reported. It is found that long-range orientational ordering in an LC phase of poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT) copolymer stabilizes a small fraction of randomly-oriented F8BT nanocrystals dispersed in an amorphous matrix of F8BT chains, resembling a self-doped host-guest system whereby excitation energy funneling and photoluminescence quantum efficiencies are enhanced significantly by triggering 3D donor-to-acceptor Förster resonance energy transfer (FRET) and dominant intrachain emission in the nano-crystal acceptor. Further, photoalignment of nematic F8BT layers is combined with LC orientational ordering to fabricate large-area-extended monodomains exhibiting >60% crystallinity and ≈20 nm-long interchain packing order. Remarkably, these monodomains demonstrate strong linearly polarized emission, whilst also promoting a new band-edge absorption species and an extra emissive interchain excited state as compared to the non-aligned films.
Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1002/advs.202407117

Authors


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Institution:
University of Oxford
Role:
Author
ORCID:
0000-0003-1828-9415
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Institution:
University of Oxford
Division:
MPLS
Department:
Engineering Science
Oxford college:
Jesus College
Role:
Author
ORCID:
0000-0001-8294-9225


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Funder identifier:
https://ror.org/01hhn8329


Publisher:
Wiley
Journal:
Advanced Science More from this journal
Volume:
11
Issue:
41
Article number:
2407117
Place of publication:
Germany
Publication date:
2024-08-29
Acceptance date:
2024-07-29
DOI:
EISSN:
2198-3844
Pmid:
39206683


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