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基于氰基二苯乙烯修饰的苯-1,3,5-三羧酸酰胺衍生物的 AIEE 超分子凝胶的荧光调控和光响应性能。

Fluorescence Regulation and Photoresponsivity in AIEE Supramolecular Gels Based on a Cyanostilbene Modified Benzene-1,3,5-Tricarboxamide Derivative.

机构信息

State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, 130012, P. R. China.

出版信息

Chemistry. 2019 Jan 2;25(1):315-322. doi: 10.1002/chem.201804135. Epub 2018 Dec 4.

Abstract

Supramolecular interactions play an important role in regulating the optical properties of molecular materials. Different arrangements of identical molecules can afford a more straightforward insight into the contributions of supramolecular interactions. Herein, a novel gelator, BTTPA, composed of a benzene-1,3,5-tricarboxamide (BTA) central unit functionalized with three cyanostilbenes is designed, which forms two kinds of gels in DMSO/water mixtures. Depending on the water volume content, the gels exhibit quite different aggregation-induced emission enhancement (AIEE) properties, with one emitting a green emission (G-gel), and the second emitting a blue emission (B-gel). The main reason for this difference is that water affects H-bonding and π-π interactions, further resulting in disparate packing modes of gelators. In addition, only the G-gel displays gel-to-sol transition accompanied with fluorescence switching according to the trans-cis photoisomerization of cyanostilbene under UV light irradiation. The B-gel does not exhibit any change because of its tight hexagonal packing arrangement. Such packing modes restricted the space in which molecules were located and inhibited the transformation of configuration of cyanostilbene. These phenomena underline the incomparable status of packing modes and molecular configuration in regulating fluorescence properties and photoresponse behavior in organic solid-state luminescent materials.

摘要

超分子相互作用在调节分子材料的光学性质方面起着重要作用。相同分子的不同排列可以更直观地了解超分子相互作用的贡献。在此,设计了一种由苯-1,3,5-三羧酸酰胺(BTA)中心单元与三个氰基取代的苯乙烯组成的新型凝胶剂 BTTPA,它在 DMSO/水混合物中形成两种凝胶。根据水的体积含量,凝胶表现出截然不同的聚集诱导发射增强(AIEE)性质,一种发出绿色发射(G-凝胶),另一种发出蓝色发射(B-凝胶)。这种差异的主要原因是水影响氢键和π-π相互作用,进一步导致凝胶剂的不同堆积方式。此外,只有 G-凝胶在紫外光照射下,根据氰基取代苯乙烯的顺反光异构化,显示出凝胶-溶胶转变伴随着荧光开关。B-凝胶由于其紧密的六方堆积排列没有任何变化。这种堆积方式限制了分子所处的空间,抑制了氰基取代苯乙烯的构象转变。这些现象强调了在调节有机固态发光材料的荧光性质和光响应行为方面,堆积方式和分子构型的不可替代性。

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