Exceptionally flexible quinodimethanes with multiple conformations: polymorph-dependent colour tone and emission of crystals
Exceptionally flexible quinodimethanes with multiple conformations: polymorph-dependent colour tone and emission of crystals
复制标题
具有多种构象的极其灵活的醌二甲烷：依赖于多晶型的色调和晶体的发射
DOI：
10.1039/d2qm01199a
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发表时间：
2023
影响因子：
7
通讯作者：
Ishigaki Yusuke
中科院分区：
文献类型：
--
作者：
Sugawara Kazuma;Ono Toshikazu;Yano Yoshio;Suzuki Takanori;Ishigaki Yusuke
四芳基醌二甲烷是一种拥挤的乙烯，可以采用多种构象，如折叠，扭曲和其他形式。然而，由于它们之间的能量差异，很难获得所有这些构象。为了解决这个问题，我们设计了灵活的多芳基取代的四氮杂蒽醌二甲烷（N4AQD），其中在过度拥挤的峡湾区域的空间位阻适度减少。结果，X射线分析显示，N4AQD不仅可以采用折叠和扭曲的形式，还可以采用中间结构，例如，平面和扭曲折叠的形式，在假多晶型。由于构象之间的电子构型有很大的差异，晶体的色调从黄色到红色变化，这取决于过度拥挤的N4AQD的构象。值得注意的是，红色到近红外发射观察到的晶体含有扭曲构象。这是第一个非常灵活的quinodimethanes与可调的物理性质和多色行为的基础上，多种构象的例子。
Tetraarylated quinodimethanes, which are one of the overcrowded ethylenes, can adopt multiple conformations, such as folded, twisted, and other forms. However, it is difficult to obtain all of these conformations due to energy differences among them. To tackle this issue, we designed flexible polyaryl-substituted tetraazaanthraquinodimethanes (N4AQDs), in which a steric hindrance in the overcrowded fjord region was moderately reduced. As a result, X-ray analyses revealed that N4AQDs could adopt not only folded and twisted forms but also intermediate structures, e.g., planar and twisted-folded forms, in pseudopolymorphs. Since there is a large difference in the electronic configuration among conformers, the colour tone of crystals varied from yellow to red depending on the conformation of overcrowded N4AQDs. Notably, red to near-infrared emission was observed for the crystal containing twisted conformers. This is the first example of exceptionally flexible quinodimethanes with tunable photophysical properties and multi-chromic behaviour based on multiple conformations.