C−H Borylation/Cross‐Coupling Forms Twisted Donor–Acceptor Compounds Exhibiting Donor‐Dependent Delayed Emission. Issue 41 (25th June 2018)

• Record Type: Journal Article
• Authors: Crossley, Daniel L.; Kulapichitr, Pakapol; Radcliffe, James E.; Dunsford, Jay J.; Vitorica‐Yrezabal, Inigo; Kahan, Rachel J.; Woodward, Adam W.; Turner, Michael L.; McDouall, Joseph J. W.; Ingleson, Michael J.
• Is Part Of: Chemistry. Volume 24:Issue 41(2018)
• Page Start: 10521
• Page End: 10530
• Publication Date: 2018-06-25
• Subjects: benzothiadiazole -- boron -- borylation -- natural transition orbitals -- thermally activated delayed fluorescence; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201801799
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Benzothiadiazole (BT) directed C−H borylation using BCl3, followed by B−Cl hydrolysis and Suzuki–Miyaura cross‐coupling enables facile access to twisted donor–acceptor compounds. A subsequent second C−H borylation step provides, on arylation of boron, access to borylated highly twisted D−A compounds with a reduced bandgap, or on B−Cl hydrolysis/cross‐coupling to twisted D‐A‐D compounds. Photophysical studies revealed that in this series there is long lifetime emission only when the donor is triphenylamine. Computational studies indicated that the key factor in observing the donor dependent long lifetime emission is the energy gap between the S1 /T2 excited states, which are predominantly intramolecular charge‐transfer states, and the T1 excited state, which is predominantly a local excited state on the BT acceptor moiety. Abstract : Directed C−H borylation and cross‐coupling provides access to twisted donor–acceptor compounds. Photophysical studies revealed long lifetime emission only when the donor is triphenylamine. Calculations indicated that the key factor in observing long lifetime emission is the energy gap between the S1 (or T2 ) excited states, which are predominantly intramolecular charge transfer (ICT) states, and the T1 excited state, which is a local excited state on benzothiadiazole acceptor unit.