卤素键驱动的聚集诱导发光骨架:盐酸-(3-(苯胺基)亚烯丙基)苯胺

Halogen Bond-Driven Aggregation-Induced Emission Skeleton: -(3-(Phenylamino)allylidene) Aniline Hydrochloride.

作者信息

Chang Yongxin, Qin Haijuan, Zhang Fusheng, Yang Zhiying, Zhang Yahui, Wang Dongdong, Bi Ce, Guo Miao, Sun Wenjing, Qing Guangyan

机构信息

CAS Key Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, People's Republic of China.

University of Chinese Academy of Sciences, Beijing 100049, People's Republic of China.

出版信息

ACS Appl Mater Interfaces. 2023 Feb 22;15(7):9751-9763. doi: 10.1021/acsami.2c21073. Epub 2023 Feb 10.

Abstract

Aggregation-induced emission (AIE) is a unique photophysical process, and its emergence brings a revolutionary change in luminescence. However, AIE-based research has been limited to a few classical molecular skeletons, which is unfavorable for in-depth studies of the photophysical characteristics of AIE and the full exploitation of their potential values. There is an urgent need to develop new skeletons to rise to the challenges of an insufficient number of AIE core structures and difficult modification. Here, we report a novel dumbbell AIE skeleton, in which two phenyls are connected through ()-3-iminoprop-1-en-1-amine. This skeleton shows extremely strong solid-state emission with an absolute quantum yield up to 69.5%, a large Stokes shift, and typical AIE characteristics, which well resolves the challenge of difficult modification and low luminous efficiency of the traditional AIE skeletons. One-step reaction, high yield, and diversified modification endow the skeleton with great scalability from simple to complicated, or from symmetrical to asymmetrical structures, which establishes the applicability of the skeleton in various scenarios. These molecules self-assemble into highly ordered layer-, rod-, petal-, hollow pipe-, or helix-like nanostructures, which contribute to strong AIE emission. Crystallographic data reveal the highly ordered layer structures of the aggregates with different substituents, and a novel halogen bond-driven self-assembly mechanism that restricts intramolecular motion is clearly discovered. Taking advantage of these merits, a full-band emission system from green to red is successfully established, which displays great potential in the construction of light-emitting films and advanced light-emitting diodes. The discovery of this AIE skeleton may motivate a huge potential application value in luminescent materials and lead to hitherto impossible technological innovations.

摘要

聚集诱导发光(AIE)是一种独特的光物理过程,它的出现给发光领域带来了革命性的变化。然而,基于AIE的研究一直局限于少数经典分子骨架,这不利于深入研究AIE的光物理特性及其潜在价值的充分挖掘。迫切需要开发新的骨架来应对AIE核心结构数量不足和修饰困难的挑战。在此,我们报道了一种新型哑铃状AIE骨架,其中两个苯基通过()-3-亚氨基丙-1-烯-1-胺相连。该骨架表现出极强的固态发光,绝对量子产率高达69.5%,斯托克斯位移大,具有典型的AIE特性,很好地解决了传统AIE骨架修饰困难和发光效率低的问题。一步反应、高产率和多样化修饰使该骨架具有从简单到复杂、从对称到不对称结构的良好可扩展性,确立了其在各种场景中的适用性。这些分子自组装成高度有序的层状、棒状、花瓣状、空心管状或螺旋状纳米结构,有助于产生强烈的AIE发光。晶体学数据揭示了不同取代基聚集体的高度有序层状结构,并清楚地发现了一种限制分子内运动的新型卤素键驱动的自组装机制。利用这些优点,成功构建了一个从绿色到红色的全波段发光体系,在发光薄膜和先进发光二极管的构建中显示出巨大潜力。这种AIE骨架的发现可能会在发光材料中激发巨大的潜在应用价值,并带来迄今为止不可能的技术创新。

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