作者:Naomi C. A. Baker、Nicholas C. Fletcher、Peter N. Horton、Michael B. Hursthouse
DOI:10.1039/c2dt12446g
日期:——
The synthesis of two new tripodal complexes [Ru(L3)](PF6)2 and [Ru(L4)](PF6)2, encapsulating a ruthenium(II) cation, has been successfully achieved and the products fully characterized, including by X-ray structural determination. The smaller cavity, built around a tris(2-aminoethyl)amido scaffold demonstrated only moderate and predictable interactions with a range of anions and no significant spectroscopic change with nitrate, chloride and bromide, although dihydrogen phosphate did result in an almost stoichiometric precipitation. The expansion of the cavity to include the more rigid 1,3,5-benzenetricarbonylamide group creates a larger cavity, which shows a decrease in the emission on the introduction of chloride, bromide, hydrogen sulfate and nitrate salts, with the 1H NMR titrations giving a surprisingly high binding affinity for nitrate over the smaller and simpler halides.
我们成功地合成了两种新的三足鼎立配合物[Ru(L3)](PF6)2 和 [Ru(L4)](PF6)2,它们都包裹着钌(II)阳离子。围绕三(2-氨基乙基)氨基支架形成的较小空腔只与一系列阴离子发生了适度的、可预测的相互作用,与硝酸盐、氯化物和溴化物的光谱变化不大,但磷酸二氢盐却产生了几乎等量的沉淀。扩大空腔以包括更坚硬的 1,3,5-苯三羰基酰胺基团会产生一个更大的空腔,在引入氯化物、溴化物、硫酸氢盐和硝酸盐时,发射率会降低,1H NMR 滴定显示硝酸盐的结合亲和力出奇地高于较小和较简单的卤化物。