Crystal structure and thermoresponsive luminescence of a 9,10-bis(phenylethynyl)anthracene-based cyclophane
Crystal structure and thermoresponsive luminescence of a 9,10-bis(phenylethynyl)anthracene-based cyclophane
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9,10-双(苯乙炔基)蒽环芳烷的晶体结构和热响应发光
DOI：
10.1039/c9me00105k
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发表时间：
2020
影响因子：
3.6
通讯作者：
Nobuyuki Tamaoki
中科院分区：
文献类型：
--
作者：
Yoshimitsu Sagara;Kiyonori Takahashi,Takayoshi Nakamura;Nobuyuki Tamaoki
在发光团中引入循环结构是实现外部刺激响应发光的一种很有前途的方法。这是因为含有柔性连接体的发光环烷倾向于形成几个分子组装态。然而，先前报道的具有热响应性和/或机械响应性发光的环烷，由于其具有柔性的环状分子结构，并没有给出适合单晶x射线结构分析的晶体。这种分析是重要的，因为解出的晶体结构可以显示出发光团的排列和光物理性质之间明确的相关性。本文报道了具有9,10-二（苯乙基）蒽基的环烷的晶体结构和热响应发光。环烷被设计成用较短的柔性低聚（乙二醇）链作为连接体连接发光基团和另一个芳香基团。两个不同的π共轭基团在单个分子中正交排列，发光团在相邻分子之间部分重叠。经室温冷却后，环烷表现为过冷向列相。对动力学捕获态的热处理导致向另一晶态的转变，从而导致光致发光颜色的变化。发射光谱研究和发射寿命测量表明，光团在过冷向列相中形成准分子，而在晶体相中没有观察到准分子的形成。
Introducing a cyclic structure to luminophores is a promising approach for achieving external stimuli-responsive luminescence. This is because luminescent cyclophanes containing flexible linkers tend to form several molecular assembled states. However, previously reported cyclophanes exhibiting thermoresponsive and/or mechanoresponsive luminescence have not given crystals suitable for single crystal X-ray structure analysis because of the flexible cyclic molecular structures. Such analysis is important because solved crystal structures can show unambiguous correlation between the arrangement of luminophores and photophysical properties. Here, we report the crystal structure of a cyclophane featuring a 9,10-bis(phenylethynyl)anthracene group and the thermoresponsive luminescence. The cyclophane was designed with shorter flexible oligo(ethyleneglycol) chains used as linkers bridging the luminophore and another aromatic group. The two different π-conjugated groups were orthogonally arranged in the individual molecule, and the luminophores partially overlapped between adjacent molecules. The cyclophane showed a supercooled nematic phase at room temperature upon cooling. Thermal treatment for the kinetically trapped state led to a transition to another crystalline state and, consequently, a change in photoluminescence colour. Emission spectroscopic studies and emission lifetime measurements revealed that the luminophores formed excimers in the supercooled nematic phase, whereas no excimer formation was observed for the crystalline phases.
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影响因子：
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DOI：
--
发表时间：
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期刊：
影响因子：
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作者：
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