Kaczmarek Anna M, Porebski Piotr W Alvarez, Mortier Tineke, Lynen Frederic, Van Deun Rik, Van Hecke Kristof
L(3) - Luminescent Lanthanide Lab, Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281-S3, B-9000 Ghent, Belgium.
Separation Science Group, Department of Organic and Macromolecular Chemistry, Ghent University, Krijgslaan 281-S4, B-9000 Ghent, Belgium.
J Inorg Biochem. 2016 Oct;163:194-205. doi: 10.1016/j.jinorgbio.2016.07.017. Epub 2016 Aug 5.
A complete series of lanthanide Schiff base salen-type complexes were prepared with trivalent lanthanide ions (Ln) and the N,N'-bis-(3-methoxysalicylidene)ethylene-1,2-diamine ligand (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu). Three unique crystal structures of La and PrN,N'-bis-(3-methoxysalicylidene)ethylene-1,2-diamine complexes, with the La complex prepared in two different synthetic approaches, are reported, namely a dimeric [La(HL)(NO)] (HL=N,N'-bis-(3-methoxysalicylidene)ethylene-1,2-diamine) complex, an asymmetric two-centered [La(HL)(NO)] complex and a discrete mononuclear [Pr(HL)(NO)(HO)] complex. For Nd and Sm, an isotypic mononuclear [Nd(HL)(NO)] and 1D polymeric [Sm(HL)(NO)(MeOH)] structure was obtained, respectively. The whole series of complexes was tested for their ability to cleave the 20-mer RNA oligonucleotide 5'-AGC-GAU-AAG-AUU-CAU-AUA-UC-3'. Additionally three complexes (Ln=Nd, Sm, Ho) were tested for the cleavage of the 12-mer RNA oligonucleotide 5'-GCA-CCC-UGU-CAG-3'. A detailed luminescence study was additionally carried out and revealed that the Eu complex emitted bright red light upon excitation at both 285.8nm and 394.4nm. The Nd, Er, and Yb complexes showed strong emission in the near-infrared region after excitation at 380nm.
用三价镧系离子（Ln）和N,N'-双（3-甲氧基水杨醛）乙二胺配体制备了一系列完整的镧系席夫碱salen型配合物（Ln = La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu）。报道了La和Pr的N,N'-双（3-甲氧基水杨醛）乙二胺配合物的三种独特晶体结构，其中La配合物通过两种不同的合成方法制备，即二聚体[La(HL)(NO)]（HL = N,N'-双（3-甲氧基水杨醛）乙二胺）配合物、不对称双中心[La(HL)(NO)]配合物和离散单核[Pr(HL)(NO)(HO)]配合物。对于Nd和Sm，分别获得了同型单核[Nd(HL)(NO)]和一维聚合物[Sm(HL)(NO)(MeOH)]结构。测试了整个系列配合物切割20聚体RNA寡核苷酸5'-AGC-GAU-AAG-AUU-CAU-AUA-UC-3'的能力。此外，测试了三种配合物（Ln = Nd、Sm、Ho）切割12聚体RNA寡核苷酸5'-GCA-CCC-UGU-CAG-3'的能力。还进行了详细的发光研究，结果表明Eu配合物在285.8nm和394.4nm激发时发出明亮的红光。Nd、Er和Yb配合物在380nm激发后在近红外区域显示出强发射。
