dc.contributor.author
Orsborne, Sarah R. E.
dc.contributor.author
Gorman, Jeffrey
dc.contributor.author
Weiss, Leah R.
dc.contributor.author
Sridhar, Akshay
dc.contributor.author
Panjwani, Naitik A.
dc.contributor.author
Divitini, Giorgio
dc.contributor.author
Budden, Peter
dc.contributor.author
Palecek, David
dc.contributor.author
Ryan, Seán T. J.
dc.contributor.author
Behrends, Jan
dc.date.accessioned
2023-04-19T11:37:48Z
dc.date.available
2023-04-19T11:37:48Z
dc.identifier.uri
https://refubium.fu-berlin.de/handle/fub188/38965
dc.identifier.uri
http://dx.doi.org/10.17169/refubium-38681
dc.description.abstract
Singlet fission (SF), an exciton-doubling process observed in certain molecular semiconductors where two triplet excitons are generated from one singlet exciton, requires correctly tuned intermolecular coupling to allow separation of the two triplets to different molecular units. We explore this using DNA-encoded assembly of SF-capable pentacenes into discrete π-stacked constructs of defined size and geometry. Precise structural control is achieved via a combination of the DNA duplex formation between complementary single-stranded DNA and the local molecular geometry that directs the SF chromophores into a stable and predictable slip-stacked configuration, as confirmed by molecular dynamics (MD) modeling. Transient electron spin resonance spectroscopy revealed that within these DNA-assembled pentacene stacks, SF evolves via a bound triplet pair quintet state, which subsequently converts into free triplets. SF evolution via a long-lived quintet state sets specific requirements on intermolecular coupling, rendering the quintet spectrum and its zero-field-splitting parameters highly sensitive to intermolecular geometry. We have found that the experimental spectra and zero-field-splitting parameters are consistent with a slight systematic strain relative to the MD-optimized geometry. Thus, the transient electron spin resonance analysis is a powerful tool to test and refine the MD-derived structure models. DNA-encoded assembly of coupled semiconductor molecules allows controlled construction of electronically functional structures, but brings with it significant dynamic and polar disorders. Our findings here of efficient SF through quintet states demonstrate that these conditions still allow efficient and controlled semiconductor operation and point toward future opportunities for constructing functional optoelectronic systems.
en
dc.format.extent
8 Seiten
dc.rights.uri
https://creativecommons.org/licenses/by/4.0/
dc.subject
Aromatic compounds
en
dc.subject
Hydrocarbons
en
dc.subject.ddc
500 Naturwissenschaften und Mathematik::540 Chemie::540 Chemie und zugeordnete Wissenschaften
dc.title
Photogeneration of Spin Quintet Triplet–Triplet Excitations in DNA-Assembled Pentacene Stacks
dc.type
Wissenschaftlicher Artikel
dcterms.bibliographicCitation.doi
10.1021/jacs.2c13743
dcterms.bibliographicCitation.journaltitle
Journal of the American Chemical Society
dcterms.bibliographicCitation.number
9
dcterms.bibliographicCitation.pagestart
5431
dcterms.bibliographicCitation.pageend
5438
dcterms.bibliographicCitation.volume
145
dcterms.bibliographicCitation.url
https://doi.org/10.1021/jacs.2c13743
refubium.affiliation
Physik
refubium.resourceType.isindependentpub
no
dcterms.accessRights.openaire
open access
dc.relation.hascorrection
https://refubium.fu-berlin.de/handle/fub188/38966
dcterms.isPartOf.eissn
1520-5126
refubium.resourceType.provider
WoS-Alert