Convenient Syntheses and Photophysical Properties of 1-Thio- and 1-Seleno-1,3-Butadiene Fluorophores in Rigid Dibenzobarrelene and Benzobarrelene Skeletons
Convenient Syntheses and Photophysical Properties of 1-Thio- and 1-Seleno-1,3-Butadiene Fluorophores in Rigid Dibenzobarrelene and Benzobarrelene Skeletons
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刚性二苯并间二烯和苯并间二烯骨架中 1-硫代-和 1-硒代-1,3-丁二烯荧光团的便捷合成和光物理性质
DOI：
10.1002/chem.201200761
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发表时间：
2012
期刊：
影响因子：
--
通讯作者：
Norio Nakata
中科院分区：
文献类型：
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作者：
Akihiko Ishii;Tatsuro Annaka;Norio Nakata
发光化合物在生物化学[1]和材料科学领域引起了相当大的关注，例如有机发光器件（OLED）。[2]近年来，几种类型的具有杂原子的荧光化合物，如硼，硅，磷和硫，已经被引入共轭体系中，[3]其中这些杂原子对相应碳对应物的HOMO和/或LUMO的电子性质提供了至关重要的扰动。这些化合物的一个显著特征是由杂原子的化学修饰引起的物理化学性质的显著变化。例如，稠合噻吩衍生物的氧化物在发射中表现出红移，并且在某些情况下，在固态下显示出比相应的未氧化衍生物更大的量子产率。[4]磷杂茂衍生物的硫属化合物或与过渡金属的配合物具有类似的性质。[5]此外，一些树枝状磷杂茂氧化物[6]显示聚集诱导发射（AIE）。[7]这些结果为含杂原子的发光化合物提供了有用的化学基础。我们最近报道了一种在刚性二苯并丁二烯骨架上带有3-亚甲基-2，3-二氢硫属元素的荧光化合物1，其中1-硫代和1-硒代-1，3-丁二烯是主要的荧光贡献者。[8]1在二氯甲烷中的荧光量子产率（FF）非常高，尽管存在一个重原子：1（E= S）为1.0，1（E= Se）为0.86.1的合成是基于分离的或中间形成的硫属金属杂环2与乙炔二甲酸二甲酯的反应。在我们的研究中，我们一直在寻求扩大1-硫族-1，3-丁二烯荧光团的取代模式，以揭示作为功能材料的潜力。因此，我们制定了一种替代的合成策略，9-蒽基部分和炔基部分之间的分子内环加成，其中在一个过程中直接构建伴随另外的环系统的二苯并巴瑞烯骨架[Eq.①]。[9]此外，这种分子内环加成有可能通过使用1-萘基作为亲炔体来合成相应的苯并巴瑞烯类似物，[10]这将提供对在巴瑞烯核心上稠合的苯环的电子和空间作用的深入了解。在这篇文章中，我们提出了1-（蒽基硫属）-或1-（萘基硫属）烯炔I（E= S，Se）的分子内[4+ 2]-环加成反应，分别合成了二苯并巴瑞烯或苯并巴瑞烯衍生物II，它们具有我们以前的方法难以获得的取代模式，并且在溶液中都是高荧光的。此外，一些硫衍生物的氧化物的性质进行了报道。
Luminescent compounds have attracted considerable attention in the fields of biochemistry [1] and materials science as exemplified by organic light-emitting devices (OLEDs).[2] In recent years, several types of fluorescent compounds with heteroatoms, such as boron, silicon, phosphorus, and sulfur, have been incorporated in conjugated systems,[3] in which these heteroatoms provide crucial perturbations to the electronic nature of the HOMO and/or the LUMO of the corresponding carbon counterparts. A significant characteristic of these compounds is the dramatic change in photophysical properties given by the chemical modification of heteroatoms. For example, oxides of fused thiophene derivatives exhibit a bathochromic shift in emissions and, in some cases, show larger quantum yields in the solid state than the corresponding unoxidized derivatives.[4] Chalcogenides or complexes with transition metals of phosphole derivatives exhibit similar properties.[5] In addition, some dendritic phosphole oxides [6] show aggregation-induced emission (AIE).[7] These outcomes provide useful chemistry for the heteroatom-containing luminescent compounds. We recently reported fluorescent compounds 1 bearing a 3-methylene-2, 3-dihydrochalcogenophene in a rigid dibenzobarrelene skeleton, in which 1-thio-and 1-seleno-1, 3-butadienes behave as the main contributor to the fluorescence.[8] The fluorescence quantum yields (FF) of 1 in dichloromethane were very high despite the presence of a heavy atom: 1.0 for 1 (E= S) and 0.86 for 1 (E= Se).The synthesis of 1 is based on the reaction of isolated or intermediately formed chalcogenametallacycles 2 with dimethyl acetylenedicarboxylate. In our studies, we have been seeking to expand the substitution patterns of the 1-chalcogeno-1, 3-butadiene fluorophores to reveal the potential as functional materials. Thus, we worked out an alternative synthetic strategy, the intramolecular cycloaddition between a 9-anthryl moiety and an alkynyl moiety, in which it is straightforward to construct the dibenzobarrelene scaffold accompanying an additional ring system in one process [Eq.(1)].[9] Furthermore, this intramolecular cycloaddition has the potential to synthesize the corresponding benzobarrelene analogues by using 1-naphthyl as the ynophile,[10] which would provide insight into the electronic and steric roles of benzene rings fused on the barrelene core. In this communication, we present the intramolecular [4+ 2]-cycloadditions of 1-(anthrylchalcogeno)-or 1-(naphthylchalcogeno) enynes I (E= S, Se) to synthesize dibenzobarrelene or benzobarrelene derivatives II, respectively, which have a substitution pattern, which was hard to obtain by our previous method, and are all highly fluorescent in solution. In addition, some of the oxide properties of the sulfur derivatives are reported.