期刊
JOURNAL OF PHYSICAL CHEMISTRY C
卷 122, 期 50, 页码 28564-28575出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.8b10867
关键词
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资金
- EPSRC [EP/L02621X/1]
- EU Horizon 2020 Grant [732013]
- EPSRC [EP/L02621X/1, EP/P012167/1] Funding Source: UKRI
Four new symmetrical donor acceptor donor (D-A-D)-type molecules are reported with diphenylamine (DPA) or 10,1l-dihydro-5H-dibenz[b,f]azepine (Az) as electron donors and 9,9-dimethylthioxanthene-S,S-dioxide (TXO2) as the electron acceptor. The donors are attached at different positions on the acceptor core: either para or meta to the sulfone unit. This series provides new insights into the effects of chromophore rigidity/flexibility on the efficiency of thermally activated delayed fluorescence (TADF). The molecules have been characterized by X-ray crystallography, by in-depth photophysical studies, and by theoretical calculations. The clear differences observed in the photophysical properties when using DPA or Az as a donor are shown to originate from different geometries of the donor unit which, in turn, influence the geometry of the nitrogen lone pair and the donating strength of the corresponding fragment. Thus, a para-substituted Az derivative demonstrated blue TADF in polar media, while the compounds with more flexible DPA units did not show delayed fluorescence. To obtain deep blue emitters, weaker donating units are needed. A more flexible donor unit leads to increased local excited state (donor) LE emission and reduced TADF. However, a certain amount of flexibility has to be present to ensure deep-blue TADF.
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