Helical Self-Assembly-Induced Singlet-Triplet Emissive Switching in a Mechanically Sensitive System.
Helical Self-Assembly-Induced Singlet-Triplet Emissive Switching in a Mechanically Sensitive System.
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DOI：
10.1021/jacs.6b10550
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发表时间：
2017-01
影响因子：
15
通讯作者：
Hongwei Wu;Yunyun Zhou;Liyuan Yin;Cheng Hang;Xin Li;H. Ågren;T. Yi;Qing Zhang;Liangliang Zhu-Lianglia
中科院分区：
文献类型：
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作者：
Hongwei Wu;Yunyun Zhou;Liyuan Yin;Cheng Hang;Xin Li;H. Ågren;T. Yi;Qing Zhang;Liangliang Zhu-Lianglia
在纳米科学中，手性已经显示出调节材料电子性质的显著能力，而将大手性引入有机光电子学的单重态-三重态特征的调节仍然是一个具有挑战性的研究课题。由于单重态和三重态激发态性质的调谐在一个单一的π功能分子连接到其荧光应用和潜在的内部量子效率的提高，我们在这里报告，超分子手性可以用来切换单重态和三重态发射在一个精心设计的螺旋形分子。以六硫代苯单荧光团为原型，通过手性α-硫辛酸侧基对其进行功能化，发现在DMF/H2O混合溶液中可以形成相应的螺旋纳米结构。在此基础上，通过螺旋自组装和解离可以实现材料的荧光和磷光之间的转换。这样的行为可以归因于一个螺旋构象依赖操纵的系统间交叉。此外，还观察到相应固体样品的可逆机械发光依赖于类似的分子自组装交替。这些结果可能为下一代超分子手性功能材料的开发提供新的思路。
In nanoscience, chirality has shown a significant ability to tune materials' electronic properties, whereas imposing macrochirality into the regulation of singlet-triplet features of organic optoelectronics remains a challenging research topic. Since the tuning for singlet and triplet excited-state properties in a single π-functional molecule connects to its multicolor luminescent application and potential improvement of internal quantum efficiency, we here report that supramolecular chirality can be employed to toggle the singlet and triplet emissions in a well-designed asterisk-shaped molecule. Employing a hexathiobenzene-based single luminophore as a prototype and functionalizing it with chiral α-lipoiate side groups, we find that helical nanoarchitectures can accordingly form in mixed DMF/H2O solution. On this basis, switching between fluorescence and phosphorescence of the material can be realized upon helical self-assembly and dissociation. Such a behavior can be attributed to a helical-conformation-dependent manipulation of the intersystem crossing. Furthermore, reversible mechanoluminescence of the corresponding solid sample was also observed to rely on an analogous molecular self-assembly alternation. These results can probably provide new visions for the development of next-generation supramolecular chiral functional materials.