Solid State and Structural Chemistry Unit, Indian Institute of Science , Bangalore 560012, India.
ACS Appl Mater Interfaces. 2018 Jan 31;10(4):3838-3847. doi: 10.1021/acsami.7b11025. Epub 2018 Jan 16.
A new class of donor-bridge-acceptor (D-π-A) π-conjugated light-emitting molecules comprising carbazole as donor and maleimide (Cbz-MI, Cbz-MI(d)), phthalimide (Cbz-Pth) as acceptor units with phenyl ring as spacer have been synthesized in good yields. These compounds exhibit high quantum yield with three distinct emission colors yellowish-green (Cbz-MI), bright yellow Cbz-MI(d), and sky blue (Cbz-Pth) in the solid state. Single-crystal X-ray and quantum chemical calculations reveals that twisting of the phenyl rings with high torsional angle on maleimide and phthalimide units reduce the effective inter-chromophore electronic coupling, furnish dramatic changes in their photophysical properties in solution and solid states. Intriguingly, Cbz-MI(d) and Cbz-Pth exhibits a unique aggregation-induced blue-shifted emission (AIBSE) due to restricted intramolecular rotation (RIR) process, while Cbz-MI shows red-shifted emission in the solid state. The solvatochromic study reveal that combined RIR and excited state migration augment AIE (aggregation-induced emission) properties. The electrochemical properties reveal that Cbz-MI exhibits high oxidation propensity while Cbz-Pth shows low reduction values. Subsequently, organic light-emitting diodes (OLEDs) were fabricated with a simple three-layer device containing Cbz-Pth and Cbz-MI(d) as emitting layers. Cbz-MI(d) exhibits high performance yellow OLED with an external quantum efficiency exceeding ∼4.1% and a brightness exceeding ∼73915 cd/m, which is among the best performance reported for bright yellow fluorescence organic light-emitting diodes.
一类新型给体-桥-受体(D-π-A)π共轭发光分子,包含咔唑作为给体和马来酰亚胺(Cbz-MI,Cbz-MI(d))、邻苯二甲酰亚胺(Cbz-Pth)作为受体单元,以苯环作为间隔基,以高产率合成。这些化合物在固态下具有高达 3 种不同发射颜色的高量子产率:黄绿色(Cbz-MI)、亮黄色(Cbz-MI(d))和天蓝色(Cbz-Pth)。单晶 X 射线和量子化学计算表明,马来酰亚胺和邻苯二甲酰亚胺单元上苯环的扭曲具有高扭转角,降低了有效发色团之间的电子耦合,导致其在溶液和固态中的光物理性质发生显著变化。有趣的是,Cbz-MI(d)和 Cbz-Pth 由于受限的分子内旋转(RIR)过程,表现出独特的聚集诱导蓝移发射(AIBSE),而 Cbz-MI 在固态下则表现出红移发射。溶剂化变色研究表明,RIR 和激发态迁移的结合增强了 AIE(聚集诱导发光)特性。电化学性质表明,Cbz-MI 表现出高氧化倾向,而 Cbz-Pth 则表现出低还原值。随后,采用包含 Cbz-Pth 和 Cbz-MI(d)作为发光层的简单三层器件制备了有机发光二极管(OLED)。Cbz-MI(d) 表现出高性能的黄色 OLED,其外量子效率超过约 4.1%,亮度超过约 73915 cd/m,这是报道的高亮度黄色荧光有机发光二极管中性能最好的之一。