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dc.contributor.authorGorman, Jeffrey
dc.contributor.authorOrsborne, Sarah RE
dc.contributor.authorSridhar, Akshay
dc.contributor.authorPandya, Raj
dc.contributor.authorBudden, Peter
dc.contributor.authorOhmann, Alexander
dc.contributor.authorPanjwani, Naitik A
dc.contributor.authorLiu, Yun
dc.contributor.authorGreenfield, Jake L
dc.contributor.authorDowland, Simon
dc.contributor.authorGray, Victor
dc.contributor.authorRyan, Seán TJ
dc.contributor.authorDe Ornellas, Sara
dc.contributor.authorEl-Sagheer, Afaf H
dc.contributor.authorBrown, Tom
dc.contributor.authorNitschke, Jonathan
dc.contributor.authorBehrends, Jan
dc.contributor.authorKeyser, Ulrich
dc.contributor.authorRao, Akshay
dc.contributor.authorCollepardo-Guevara, Rosana
dc.contributor.authorStulz, Eugen
dc.contributor.authorFriend, Richard
dc.contributor.authorAuras, Florian
dc.description.abstractNatural photosystems use protein scaffolds to control intermolecular interactions that enable exciton flow, charge generation, and long-range charge separation. In contrast, there is limited structural control in current organic electronic devices such as OLEDs and solar cells. We report here the DNA-encoded assembly of π-conjugated perylene diimides (PDIs) with deterministic control over the number of electronically coupled molecules. The PDIs are integrated within DNA chains using phosphoramidite coupling chemistry, allowing selection of the DNA sequence to either side, and specification of intermolecular DNA hybridization. In this way, we have developed a "toolbox" for construction of any stacking sequence of these semiconducting molecules. We have discovered that we need to use a full hierarchy of interactions: DNA guides the semiconductors into specified close proximity, hydrophobic-hydrophilic differentiation drives aggregation of the semiconductor moieties, and local geometry and electrostatic interactions define intermolecular positioning. As a result, the PDIs pack to give substantial intermolecular π wave function overlap, leading to an evolution of singlet excited states from localized excitons in the PDI monomer to excimers with wave functions delocalized over all five PDIs in the pentamer. This is accompanied by a change in the dominant triplet forming mechanism from localized spin-orbit charge transfer mediated intersystem crossing for the monomer toward a delocalized excimer process for the pentamer. Our modular DNA-based assembly reveals real opportunities for the rapid development of bespoke semiconductor architectures with molecule-by-molecule precision.
dc.description.sponsorshipERC Horizon 2020 (grant agreement No 670405 and No 803326) EPSRC Tier-2 capital grant EP/P020259/1. Winton Advanced Research Programme for the Physics of Sustainability. Simons Foundation (Grant 601946). Swedish research council, Vetenskapsrådet 2018-00238
dc.publisherAmerican Chemical Society (ACS)
dc.rightsAttribution-NonCommercial-NoDerivatives 4.0 International
dc.titleDeoxyribonucleic Acid Encoded and Size-Defined π-Stacking of Perylene Diimides.
prism.publicationNameJ Am Chem Soc
dc.contributor.orcidGorman, Jeffrey [0000-0002-6888-7838]
dc.contributor.orcidPandya, Raj [0000-0003-1108-9322]
dc.contributor.orcidOhmann, Alexander [0000-0003-3537-1074]
dc.contributor.orcidPanjwani, Naitik A [0000-0002-2913-5377]
dc.contributor.orcidLiu, Yun [0000-0003-1630-4052]
dc.contributor.orcidGray, Victor [0000-0001-6583-8654]
dc.contributor.orcidEl-Sagheer, Afaf H [0000-0001-8706-1292]
dc.contributor.orcidBrown, Tom [0000-0002-6538-3036]
dc.contributor.orcidNitschke, Jonathan [0000-0002-4060-5122]
dc.contributor.orcidBehrends, Jan [0000-0003-1024-428X]
dc.contributor.orcidKeyser, Ulrich [0000-0003-3188-5414]
dc.contributor.orcidRao, Akshay [0000-0003-4261-0766]
dc.contributor.orcidCollepardo-Guevara, Rosana [0000-0003-1781-7351]
dc.contributor.orcidStulz, Eugen [0000-0002-5302-2276]
dc.contributor.orcidFriend, Richard [0000-0001-6565-6308]
dc.contributor.orcidAuras, Florian [0000-0003-1709-4384]
rioxxterms.typeJournal Article/Review
pubs.funder-project-idEuropean Research Council (670405)
pubs.funder-project-idEngineering and Physical Sciences Research Council (EP/P020259/1)
pubs.funder-project-idEuropean Research Council (803326)
cam.orpheus.successTue Feb 01 19:02:20 GMT 2022 - The item has an open VoR version.*

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Attribution-NonCommercial-NoDerivatives 4.0 International
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