905966-37-2Relevant articles and documents
Deoxyribonucleic Acid Encoded and Size-Defined π-Stacking of Perylene Diimides
Auras, Florian,Behrends, Jan,Brown, Tom,Budden, Peter,Collepardo-Guevara, Rosana,De Ornellas, Sara,Dowland, Simon,El-Sagheer, Afaf H.,Friend, Richard H.,Gorman, Jeffrey,Gray, Victor,Greenfield, Jake L.,Keyser, Ulrich F.,Liu, Yun,Nitschke, Jonathan R.,Ohmann, Alexander,Orsborne, Sarah R. E.,Pandya, Raj,Panjwani, Naitik A.,Rao, Akshay,Ryan, Seán T. J.,Sridhar, Akshay,Stulz, Eugen
supporting information, (2022/01/08)
Natural 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 πwave 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.
Transition-Metal-Free ipso-Trifluoromethylthiolation of Lithium Aryl Boronates
Shen, Feng,Zheng, Hanliang,Xue, Xiao-Song,Lu, Long,Shen, Qilong
supporting information, p. 6347 - 6351 (2019/08/20)
A transition-metal-free direct trifluoromethylthiolation of the ipso-carbon of lithium aryl boronates with trifluoromethanesulfenate under mild conditions was described. In addition, late-stage site-selective C-H borylation/trifluoromethylation and C-Cl b
Transition-Metal-Free, Visible-Light-Enabled Decarboxylative Borylation of Aryl N-Hydroxyphthalimide Esters
Candish, Lisa,Teders, Michael,Glorius, Frank
supporting information, p. 7440 - 7443 (2017/06/13)
Herein, we report a conceptually novel borylation reaction proceeding via a mild photoinduced decarboxylation of redox-activated aromatic carboxylic acids. This work constitutes the first application of cheap and easily prepared N-hydroxyphthalimide esters as aryl radical precursors and does not require the use of expensive transition metals or ligands. The reaction is operationally simple, scalable, and displays broad scope and functional group tolerance.
