Solid-state gas sensors developed from functional difluoroboradiazaindacene dyes.
Solid-state gas sensors developed from functional difluoroboradiazaindacene dyes.
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DOI：
10.1002/chem.200801911
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发表时间：
2009-01
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影响因子：
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通讯作者：
R. Ziessel;G. Ulrich;A. Harriman;Mohammed A. H. Alamiry;B. Stewart;P. Retailleau
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文献类型：
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作者：
R. Ziessel;G. Ulrich;A. Harriman;Mohammed A. H. Alamiry;B. Stewart;P. Retailleau
本文介绍了几种新型二氟硼二氮二烯（BODIPY）染料的合成和表征，这些染料在中心8位由苯基氧基、苯基庚酸酯或苯基庚酸片段官能化，在3位或3/5位由4-二甲氨基苯基苯乙烯基残基官能化。单晶结构的测定证实了染料的平面性，而吸收和荧光光谱性质对末端苯胺给基的质子化（或烷基化）状态高度敏感。可逆的颜色调整，从绿色到蓝色的吸收和从无色（即，近红外区域）到红色的荧光是获得连续添加酸和碱。双官能化衍生物在这方面特别有趣，在乙腈中显示出两个良好分辨的pK(a)值为5.10和3.04。第一个质子的加入只引起很小的光谱变化，并且在第二个质子加入时使分子失活。由于这种类型的染料固有的分子内电荷转移特性的可逆消失，正是后一步骤适应了吸收和发射特性的巨大变化。这项工作的主要重点是将染料的共价锚定在惰性的多孔聚丙烯酸酯珠上，从而形成适合分析气体或流动液体的固态传感器。最终的材料是高度稳定的——它的性能在一年多后不会下降——并且在许多循环中完全可逆。灵敏度如此之高，以至于反应可以用肉眼观察到，对HCl的检测限约为600 ppb，对氨的检测限约为80 ppb。可以检测到微量的双光气，也可以检测到烷基化剂。感应作用是不分青红皂白的，并且当珠子分散在水介质中时也起作用。
This article describes the synthesis and characterization of several new difluoroboradiazaindacene (BODIPY) dyes functionalized at the central 8-position by a phenyliodo, phenylheptynoate or phenylheptynoic fragment and at the 3- or 3/5-position(s) by 4-dimethylaminophenylstyryl residue(s). Single-crystal structural determinations confirm the planarity of the dyes, while the absorption and fluorescence spectroscopic properties are highly sensitive to the state of protonation (or alkylation) of the terminal anilino donor group(s). Reversible color tuning from green to blue for absorption and from colorless (i.e., near-IR region) to red for fluorescence is obtained on successive addition of acid and base. The difunctionalized derivative is especially interesting in this respect and shows two well-resolved pK(a) values of 5.10 and 3.04 in acetonitrile. Addition of the first proton causes only small spectral changes and deactivates the molecule towards addition of the second proton. It is this latter step that accommodates the large change in absorption and emission properties, due to the reversible extinction of the intramolecular charge-transfer character inherent to this type of dye. The main focus of the work is the covalent anchoring of the dyes to inert, porous polyacrylate beads so as to form a solid-state sensor suitable for analysis of gases or flowing liquids. The final material is highly stable--its performance is undiminished after more than one year--and fully reversible over many cycles. The sensitivity is such that reactions can be followed by the naked eye and the detection limit is about 600 ppb for HCl and about 80 ppb for ammonia. Trace amounts of diphosgene can be detected, as can alkylating agents. The sensing action is indiscriminate and also operates when the beads are dispersed in aqueous media.