Chemistry Department, Firat University, 23169, Elazig, Turkey.
Talanta. 2003 Feb 6;59(2):303-9. doi: 10.1016/s0039-9140(02)00504-0.
The complexing of Eu(fod)(3) with macrocyclic ethers, benzo[15]crown-5, benzo[12]crown-4, dibenzo[20]crown-6, dibenzo[23]crown-7 and dibenzo[26]crown-8 was observed on their (1)H-NMR spectra and the selective binding constants at 400 MHz and 305 K in CDCl(3) were reported. The Eu(fod)(3) interaction displayed the selective binding role of oxygen on macrocyclic, H(2)COCH(2), backbones with o- or m-dioxyphenyl groups referring the (1)H chemical shifts. The estimated equilibrium constants, K(a) of 1:1 ratio of interactions were in accordance with the Eu(3+) ionic radii to bind the oxygen sites depending on the macrocyclic size and conformation of the ethers. The minimum lanthanide-macrocyclic ether distance displayed the maximum stability so that benzo[3n]crown-n (n=4, 5) group was found to bind the Eu(fod)(3) moderately whilst dibenzo[3n+2]crown-n (n=6-8) oligomer chemical shifts were induced largely since the such Eu(3+) complexes are more stable with larger ethyleneoxy groups.
Eu(fod)3 与大环醚,苯并[15]冠-5、苯并[12]冠-4、二苯并[20]冠-6、二苯并[23]冠-7 和二苯并[26]冠-8 的络合作用在其(1)H-NMR 谱中观察到,并在 400 MHz 和 305 K 下在 CDCl3 中报告了选择性结合常数。Eu(fod)3 相互作用显示了大环、H2COCH2 骨架上氧的选择性结合作用,带有邻或间二氧苯基基团,参考(1)H 化学位移。估计的平衡常数,K(a)为 1:1 比例的相互作用与根据大环尺寸和醚的构象结合氧位的 Eu(3+)离子半径一致。最小的镧系元素-大环醚距离显示出最大的稳定性,因此苯并[3n]冠-n(n=4,5)基团被发现适度结合 Eu(fod)3,而二苯并[3n+2]冠-n(n=6-8)齐聚物化学位移则被大大诱导,因为此类 Eu(3+)配合物具有更大的乙撑氧基团而更加稳定。