A red-emissive aminobenzopyrano-xanthene dye: elucidation of fluorescence emission mechanisms in solution and in the aggregate state.
A red-emissive aminobenzopyrano-xanthene dye: elucidation of fluorescence emission mechanisms in solution and in the aggregate state.
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DOI：
10.1039/c2cp43503a
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发表时间：
2013-01
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通讯作者：
Shinichiro Kamino;A. Muranaka;Miho Murakami;Asana Tatsumi;N. Nagaoka;Y. Shirasaki;Keiko Watanabe;Kengo Yoshida;Jun Horigome;S. Komeda;M. Uchiyama;S. Enomoto
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作者：
Shinichiro Kamino;A. Muranaka;Miho Murakami;Asana Tatsumi;N. Nagaoka;Y. Shirasaki;Keiko Watanabe;Kengo Yoshida;Jun Horigome;S. Komeda;M. Uchiyama;S. Enomoto
我们设计并合成了一类具有扩展的ABPX01共轭体系的新型罗丹明染料，命名为3‘，3’‘-bis(oxospiroisobenzofuran)-3，7-bis(diethylamino)benzopyrano-xanthene(π)染料。ABPX01在稀溶液和聚集态都表现出荧光发射，而传统的罗丹明染料表现出聚集诱导猝灭(AIQ)。通过分光光度测定和密度泛函理论(DFT)计算确定了ABPX01在溶液中的化学物种，研究了化学物种、颜色和荧光发射之间的关系。ABPX01有多种形式：螺内酯形式(ABPX01(0))，无色；以及单阳离子形式(ABPX01H(+))和阳离子形式(ABPX01H(2)(2+))，有色。通过对一对螺内酯苯环的不同取向，分离了反式和顺式ABPX01(0)的立体异构体，并测定了它们的晶体结构。ABPX01H(2)(2+)为红色荧光物质。详细的光谱和电子显微镜研究表明，ABPX01H(2)(2+)在HCl水溶液中与氯(-)形成离子缔合物，ABPX01盐酸盐的纳米和亚微米级胶体聚集体具有荧光发射。为了进一步验证聚集诱导发射增强(AIEE)的机理，合成了ABPX01盐酸盐，并在粉末状态下类似地检测了它的荧光。ABPX01中的AIE可能是由于空间位阻离子缔合物和羧基苯基对染料相互作用诱导的二聚体形成的限制，以及黄原烯部分的结构刚性和分子间排列的协同作用所致。我们希望ABPX染料的设计策略将扩展到开发具有合适的荧光发射控制机制的各种功能有机染料基荧光团(ODF)，以便在新的电致发光器件中应用。
We have designed and synthesized a new class of rhodamine dyes with an extended π-conjugated system and named them 3',3''-bis(oxospiroisobenzofuran)-3,7-bis(diethylamino)benzopyrano-xanthene (ABPX01) dyes. ABPX01 exhibits fluorescence emission in both dilute solution and the aggregate state, whereas conventional rhodamine dyes show aggregation-induced quenching (AIQ). The chemical species of ABPX01 in solution were determined by spectrophotometric measurements and density functional theory (DFT) calculations to study the relationship among chemical species, color, and fluorescence emission. ABPX01 has various forms: the spirolactone form (ABPX01(0)), which is colorless; and the monocationic form (ABPX01H(+)) and the dicationic form (ABPX01H(2)(2+)), which are colored. By orienting a pair of spirolactone benzene moieties differently, the stereoisomers of trans- and cis-ABPX01(0) were separated and their crystal structures determined. ABPX01H(2)(2+) was identified to be a red fluorescent species. Detailed spectroscopic and electron microscopic investigations led to the assumption that the ABPX01H(2)(2+) formed ion associates with Cl(-) as counter anions in HCl aqueous solution, and the nano- and submicrometer-sized colloidal aggregates of ABPX01 hydrochloride exhibit fluorescence emission. To further verify the aggregation-induced emission enhancement (AIEE) mechanism, ABPX01 hydrochloride was synthesized and its fluorescence was similarly checked in the powder state. AIEE in ABPX01 might be attributed to the synergistic combination of the restriction of dye-dye interaction induced dimer formation by sterically hindered ion associates and carboxylic benzene moieties, and the structural rigidity and intermolecular arrangement of the xanthene moiety. We expect that the design strategy of ABPX dyes will be extended to the development of a wide variety of functional organic-dye-based fluorophores (ODFs) with suitable fluorescence-emission controlled mechanisms for many useful applications in new electroluminescent devices.