Solid-emissive fluorophores constructed by a non-planar heteropolycyclic structure with bulky substituents: synthesis and X-ray crystal structures.
Solid-emissive fluorophores constructed by a non-planar heteropolycyclic structure with bulky substituents: synthesis and X-ray crystal structures.
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DOI：
10.1039/b700848a
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发表时间：
2007-04
影响因子：
3.2
通讯作者：
Y. Ooyama;Shintaro Yoshikawa;Shigeru Watanabe;Katsuhira Yoshida
中科院分区：
文献类型：
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作者：
Y. Ooyama;Shintaro Yoshikawa;Shigeru Watanabe;Katsuhira Yoshida
设计并合成了具有非平面结构的茚并[1，2-B]苯并[4，5-e]吡喃-11-酮类固体发光材料。在1，4-二氧六环中的荧光量子产率为（Phi = 0.053）>>（Phi = 0.013）>（Phi = 0.003）。另一方面，荧光团的固态荧光量子产率为（Phi = 0.39）>（Phi = 0.15）>（Phi = 0.06）。为了阐明在溶液中的量子产率的巨大差异，并在固态和荧光团之间，我们进行了时间分辨荧光光谱测量，半经验分子轨道计算（AM 1和INDO/S），和X射线晶体学分析。的辐射和非辐射的速率常数的值的比较，确定的时间分辨光谱测量在溶液中，并在结晶状态下的支持，非辐射衰减减少的限制的旋转的苯基和噻吩基环在固态。此外，X射线晶体结构表明，在和中，具有空间位阻取代基的非平面结构防止荧光团形成短的π-π接触，并产生强的固态荧光。另一方面，在的晶体中，发现相邻荧光团之间形成连续的分子间CH[dot dot dot]S键合增加短π-π接触并降低荧光强度。
Novel solid-emissive indeno[1,2-b]benzo[4,5-e]pyran-11-one-type fluorophores having non-planar structures with sterically hindered substituents (R = butyl, phenyl, and thienyl) have been designed and conveniently synthesized. The fluorescence quantum yields of in 1,4-dioxane were (Phi = 0.053) >> (Phi = 0.013) > (Phi = 0.003). On the other hand, the solid-state fluorescence quantum yields of the fluorophores were (Phi = 0.39) > (Phi = 0.15) > (Phi = 0.06). To elucidate the large differences in the quantum yields in solution and in the solid state and among the fluorophores , we performed time-resolved fluorescence spectroscopic measurements, semi-empirical molecular orbital calculations (AM1 and INDO/S), and X-ray crystallographic analyses of . The comparison of the values of the radiative and non-radiative rate constants determined by the time-resolved spectroscopic measurements in solution and in the crystalline state supported that non-radiative decay is reduced by restriction of the rotation of the phenyl and thienyl rings in the solid state. In addition, the X-ray crystal structures demonstrated that, in and , the non-planar structure with sterically hindered substituents prevents the fluorophores from forming short pi-pi contacts and produces strong solid-state fluorescence. On the other hand, in the crystal of , the formation of continuous intermolecular CH[dot dot dot]S bonding between neighboring fluorophores was found to increase short pi-pi contacts and reduce the fluorescence intensity.