二氟硼姜黄素烯丙基醚的合成及Pd(0)荧光探针性质研究

Synthesis of difluoroboron curcumin allylic ether and its application as fluorescent sensor for palladium(0)

钯(Pd)是一种性质非常特殊的稀有过渡金属,在化学以及材料科学中具有重要地位.钯催化反应的产物中常有一定浓度的残余钯污染,需要进一步纯化和检测.因此发展用于检测Pd的技术手段很有必要.零价钯可以通过对烯丙基氧化插入而切断烯丙基醚类化合物的C—O键.基于这个反应,设计合成了荧光分子二氟硼姜黄素烯丙基醚化合物,并测试了其紫外光谱和荧光光谱,研究了其对钯化合物的选择性识别作用.结果表明,该荧光分子对二价钯并无响应,只有零价钯Pd2(dba)3使该分子荧光发生猝灭.该荧光分子对于零价钯表现出很好的选择性和响应性,可作为基于脱烯丙基化反应检测零价Pd的荧光探针,为"turn-off"型荧光探针.

Palladium is a rare transition metal that plays a pivotal role in materials and chemistry. Pd-catalyzed reactions often produce materials contaminated with Pd at a much higher level requiring extensive purifications and ana lyses. Therefore, it is of great significance to develop new methods for monitoring palladium. Pd（0） is capable of catalyzing the allylic oxidative insertion to cleave the allylic C--O bond of allylic ethers. Based on this reaction, difluoroboron cureumin allylic ether （BF2-curcumin-OAllyl） was designed and synthesized. Its Uv-Vis and fluorescence spectra were measured. The influence of palladium compounds on its fluorescence properties was examined. The results showed that no spectrum change was observed for Pd（II） compounds. However, the addition of Pd2 （dba）a in the curcumin solution leaded to a fluorescent quenching, so it is a ＂turn-off＂ type probe. BF2 eurcumin OAllyl is a Pd（0） sensor with good selectivity and sensitivity and can be utilized as a fluorescent probe for Pd（0） based on the O-deallylation reaction.