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Synthesis, self-assembly and optical properties of some rigid π-bridged triphenylene dimers
Journal of Materials Chemistry C ( IF 5.7 ) Pub Date : 2022-09-02 , DOI: 10.1039/d2tc02441a Hang Lin 1 , Ke-Xiao Zhao 1 , Min Jing 1 , Xiu-Hai Long 1 , Ke-Qing Zhao 1 , Ping Hu 1 , Bi-Qin Wang 1 , Peng Lei 2 , Qing-Dao Zeng 2 , Bertrand Donnio 3
Journal of Materials Chemistry C ( IF 5.7 ) Pub Date : 2022-09-02 , DOI: 10.1039/d2tc02441a Hang Lin 1 , Ke-Xiao Zhao 1 , Min Jing 1 , Xiu-Hai Long 1 , Ke-Qing Zhao 1 , Ping Hu 1 , Bi-Qin Wang 1 , Peng Lei 2 , Qing-Dao Zeng 2 , Bertrand Donnio 3
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The synthesis of an exclusive family of liquid-crystalline dimers consisting of two protomesogenic triphenylene moieties connected via a rigid, π-conjugated bridge, and the study of their mesomorphous, gel self-assembly and optical properties as a function of the nature of the bridge are reported. Various triphenylene bridged dimers were successfully prepared by either palladium-catalyzed Suzuki–Miyaura cross-coupling between pentakis(alkoxy)triphenylene nonaflates and various commercially accessible aryldiboronic acids (as bridges) or by FeCl3-promoted Scholl oxidative homo-coupling of thiophene/thienothiophene/furan-containing pentakis(alkoxy)triphenylene derivatives. All linear dimers are mesomorphous, and self-organize into large multi-columnar rectangular superlattices, with columnar pairs arranged according to a chevron-like pattern, as deduced from SWAXS and supported by STM. At high temperature, most compounds also display a nematic columnar mesophase (NCol), easily recognized by characteristic optical textures. The transition temperature and mesophase ranges show a high dependency on the bridge nature and, to a lesser extent, on the chain-lengths around the triphenylene moieties. The sole kinked bridged-dimeric homolog of this series exhibits a single, room-temperature hexagonal mesophase (Colhex), as do the monofunctionalized triphenylene precursors, whereas the dimeric triphenylene with no bridge is not mesomorphous. UV-visible absorption and fluorescence emission spectra were measured in both solvents and thin films. The π-conjugated bridged-dimers exhibit emission spanning from 400–700 nm, thus covering the full visible-light range, whose emission maxima are obviously influenced by the chemical nature of the bridge. Furthermore, fluorescence quantum yields as high as 64% were measured for some of them. DFT theoretical computing calculations fully support the experimental measurements. Most dimers also form gels in cyclohexane and emit blue-to-orange light when irradiated by UV light; the corresponding xerogels revealed that their gelation ability results from the 3D morphology of entangled ultra-long and thin microfibers. The facile synthesis of these unique, multifunctional rigid discotic dimers, their rich mesomorphism, strong gelation ability and fine-tuned photophysical properties make these materials very attractive for the active field of organic electronics.
中文翻译：
一些刚性π桥联苯并苯二聚体的合成、自组装和光学性质
合成由两个通过刚性 π 共轭桥连接的质子间原三亚苯基部分组成的独家液晶二聚体家族，并研究它们的介晶、凝胶自组装和光学性质作为桥性质的函数被报道。通过钯催化的 Suzuki-Miyaura 在五（烷氧基）三苯并苯二甲酸酯和各种商业上可获得的芳基二硼酸（作为桥）之间的交叉偶联或通过 FeCl 3成功制备了各种三苯桥二聚体-促进了噻吩/噻吩并噻吩/呋喃的含五（烷氧基）苯并苯衍生物的 Scholl 氧化同源偶联。所有线性二聚体都是介晶的，并且自组织成大的多柱矩形超晶格，柱状对按照人字形图案排列，由 SWAXS 推导出并由 STM 支持。在高温下，大多数化合物还显示向列柱状中间相 (N Col )，很容易通过特征光学纹理识别。转变温度和中间相范围高度依赖于桥的性质，并且在较小程度上依赖于三亚苯基部分周围的链长。该系列的唯一扭结桥联二聚体同系物表现出单一的室温六角中间相（Col hex)，单官能化的苯并苯前体也是如此，而没有桥的二聚苯并苯不是介晶的。在溶剂和薄膜中测量紫外-可见吸收和荧光发射光谱。π-共轭桥接二聚体的发射范围为 400-700 nm，因此覆盖了整个可见光范围，其发射最大值明显受桥的化学性质的影响。此外，测量到其中一些的荧光量子产率高达 64%。DFT 理论计算计算完全支持实验测量。大多数二聚体还在环己烷中形成凝胶，并在受到紫外线照射时发出蓝色至橙色的光；相应的干凝胶表明，它们的凝胶化能力源于纠缠的超长和细微纤维的 3D 形态。
更新日期：2022-09-02
中文翻译：
一些刚性π桥联苯并苯二聚体的合成、自组装和光学性质
合成由两个通过刚性 π 共轭桥连接的质子间原三亚苯基部分组成的独家液晶二聚体家族，并研究它们的介晶、凝胶自组装和光学性质作为桥性质的函数被报道。通过钯催化的 Suzuki-Miyaura 在五（烷氧基）三苯并苯二甲酸酯和各种商业上可获得的芳基二硼酸（作为桥）之间的交叉偶联或通过 FeCl 3成功制备了各种三苯桥二聚体-促进了噻吩/噻吩并噻吩/呋喃的含五（烷氧基）苯并苯衍生物的 Scholl 氧化同源偶联。所有线性二聚体都是介晶的，并且自组织成大的多柱矩形超晶格，柱状对按照人字形图案排列，由 SWAXS 推导出并由 STM 支持。在高温下，大多数化合物还显示向列柱状中间相 (N Col )，很容易通过特征光学纹理识别。转变温度和中间相范围高度依赖于桥的性质，并且在较小程度上依赖于三亚苯基部分周围的链长。该系列的唯一扭结桥联二聚体同系物表现出单一的室温六角中间相（Col hex)，单官能化的苯并苯前体也是如此，而没有桥的二聚苯并苯不是介晶的。在溶剂和薄膜中测量紫外-可见吸收和荧光发射光谱。π-共轭桥接二聚体的发射范围为 400-700 nm，因此覆盖了整个可见光范围，其发射最大值明显受桥的化学性质的影响。此外，测量到其中一些的荧光量子产率高达 64%。DFT 理论计算计算完全支持实验测量。大多数二聚体还在环己烷中形成凝胶，并在受到紫外线照射时发出蓝色至橙色的光；相应的干凝胶表明，它们的凝胶化能力源于纠缠的超长和细微纤维的 3D 形态。
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