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Multi-stimuli responsive luminescent azepane-substituted β-diketones and difluoroboron complexes†
Materials Chemistry Frontiers ( IF 6.0 ) Pub Date : 2017-05-25 00:00:00 , DOI: 10.1039/c7qm00137a Fang Wang 1 , Christopher A DeRosa 1 , Margaret L Daly 1 , Daniel Song 1 , Cassandra L Fraser 1
Materials Chemistry Frontiers ( IF 6.0 ) Pub Date : 2017-05-25 00:00:00 , DOI: 10.1039/c7qm00137a Fang Wang 1 , Christopher A DeRosa 1 , Margaret L Daly 1 , Daniel Song 1 , Cassandra L Fraser 1
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Difluoroboron β-diketonate (BF2bdk) compounds show environment-sensitive optical properties in solution, aggregation-induced emission (AIE) and multi-stimuli responsive fluorescence switching in the solid state. Here, a series of 4-azepane-substituted β-diketone (bdk) ligands (L-H, L-OMe, L-Br) and their corresponding difluoroboron dyes (D-H, D-OMe, D-Br) were synthesized, and various responsive fluorescence properties of the compounds were studied, including solvatochromism, viscochromism, AIE, mechanochromic luminescence (ML) and halochromism. Compared to the β-diketones, the boron complexes exhibited higher extinction coefficients but lower quantum yields, and red-shifted absorption and emission in CH2Cl2. Computational studies showed that intramolecular charge transfer (ICT) dominated rather than π–π* transitions in all the compounds regardless of boron coordination. In solution, all the bdk ligands and boron dyes showed red-shifted emission in more polar solvents and increased fluorescence intensity in more viscous media. Upon aggregation, the emission of the β-diketones was quenched, however, the boronated dyes showed increased emission, indicative of AIE. Solid-state emission properties, ML and halochromism, were investigated on spin cast films. For ML, smearing caused a bathochromic emission shift for L-Br, and powder X-ray diffraction (XRD) patterns showed that the “as spun” and thermally annealed states were more crystalline and the smeared state was amorphous. No obvious ML emission shift was observed for L-H or L-OMe, and the boronated dyes were not mechano-active. Trifluoroacetic acid (TFA) and triethylamine (TEA) vapors were used to study halochromism. Large hypsochromic emission shifts were observed for all the compounds after exposure to TFA vapor, and reversible fluorescence switching was achieved using the acid/base pair.
中文翻译：
多重刺激响应发光氮杂环庚烷取代的 β-二酮和二氟硼复合物†
二氟硼 β-二酮 (BF 2 bdk) 化合物在溶液中表现出环境敏感的光学特性，在固态中表现出聚集诱导发射 (AIE) 和多刺激响应荧光切换。在此，合成了一系列4-氮杂环庚烷取代的β-二酮（bdk）配体（LH、L-OMe、L-Br）及其相应的二氟硼染料（DH、D-OMe、D-Br），并合成了各种响应性的染料。研究了化合物的荧光性质，包括溶剂致变色、粘致变色、AIE、机械致色发光（ML）和卤致变色。与β-二酮相比，硼配合物表现出较高的消光系数，但较低的量子产率，并且在CH 2 Cl 2中的吸收和发射发生红移。计算研究表明，无论硼配位如何，所有化合物中均以分子内电荷转移 (ICT) 而非 π-π* 跃迁为主。在溶液中，所有 bdk 配体和硼染料在极性较大的溶剂中显示出红移发射，并在较粘稠的介质中显示出增加的荧光强度。聚集后，β-二酮的发射被猝灭，然而，硼化染料显示出发射增加，表明 AIE。研究了旋涂薄膜的固态发射特性、ML 和卤色现象。对于 ML，弥散导致L-Br发生红色发射位移，粉末 X 射线衍射 (XRD) 图案显示“旋转”状态和热退火状态更多地结晶，而弥散状态是非晶态。LH或L-OMe没有观察到明显的 ML 发射位移，并且硼化染料不具有机械活性。三氟乙酸 (TFA) 和三乙胺 (TEA) 蒸气用于研究卤色现象。暴露于 TFA 蒸气后，所有化合物均观察到较大的低致色发射位移，并且使用酸/碱对实现了可逆荧光切换。
更新日期：2017-05-25
中文翻译：
多重刺激响应发光氮杂环庚烷取代的 β-二酮和二氟硼复合物†
二氟硼 β-二酮 (BF 2 bdk) 化合物在溶液中表现出环境敏感的光学特性，在固态中表现出聚集诱导发射 (AIE) 和多刺激响应荧光切换。在此，合成了一系列4-氮杂环庚烷取代的β-二酮（bdk）配体（LH、L-OMe、L-Br）及其相应的二氟硼染料（DH、D-OMe、D-Br），并合成了各种响应性的染料。研究了化合物的荧光性质，包括溶剂致变色、粘致变色、AIE、机械致色发光（ML）和卤致变色。与β-二酮相比，硼配合物表现出较高的消光系数，但较低的量子产率，并且在CH 2 Cl 2中的吸收和发射发生红移。计算研究表明，无论硼配位如何，所有化合物中均以分子内电荷转移 (ICT) 而非 π-π* 跃迁为主。在溶液中，所有 bdk 配体和硼染料在极性较大的溶剂中显示出红移发射，并在较粘稠的介质中显示出增加的荧光强度。聚集后，β-二酮的发射被猝灭，然而，硼化染料显示出发射增加，表明 AIE。研究了旋涂薄膜的固态发射特性、ML 和卤色现象。对于 ML，弥散导致L-Br发生红色发射位移，粉末 X 射线衍射 (XRD) 图案显示“旋转”状态和热退火状态更多地结晶，而弥散状态是非晶态。LH或L-OMe没有观察到明显的 ML 发射位移，并且硼化染料不具有机械活性。三氟乙酸 (TFA) 和三乙胺 (TEA) 蒸气用于研究卤色现象。暴露于 TFA 蒸气后，所有化合物均观察到较大的低致色发射位移，并且使用酸/碱对实现了可逆荧光切换。
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