Liew Jane Y, Brown Joshua J, Moore Evan G, Schwalbe Matthias
School of Chemistry and Molecular Biosciences, The University of Queensland, St. Lucia, Queensland, 4072, Australia.
Institute of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Strasse 2, 12489, Berlin, Germany.
Chemistry. 2016 Nov 2;22(45):16178-16186. doi: 10.1002/chem.201602189. Epub 2016 Sep 26.
An asymmetric 'Pacman' metalloligand, [Zn(PXT)], which features a cofacial Zn -porphyrin unit (P) covalently attached to a terpyridine (T) chelating group via a rigid xanthene (X) moiety has been prepared, and its interactions with several different trivalent Ln cations (Nd , Gd , Yb and Lu ) have been examined. The formation of 1:1 metal-ligand complexes was monitored by H NMR spectroscopy and corroborated by HRMS data. Solution-stability constants were determined by UV/Vis titration, and the resulting complexes with Nd or Yb demonstrated sensitised emission in the NIR region due to energy transfer from the Zn -porphyrin donor to Ln acceptor. The energy transfer was investigated by transient absorption techniques, which provided insight into the kinetics and efficiency of the antenna effect.
已制备出一种不对称的“吃豆人”金属配体[Zn(PXT)]，其特征在于通过刚性的氧杂蒽（X）部分将共面的锌卟啉单元（P）共价连接到三联吡啶（T）螯合基团上，并研究了它与几种不同的三价镧系阳离子（Nd、Gd、Yb和Lu）的相互作用。通过1H NMR光谱监测1:1金属-配体配合物的形成，并通过高分辨质谱数据进行确证。通过紫外/可见滴定法测定溶液稳定性常数，所得与Nd或Yb的配合物由于从锌卟啉供体到镧系受体的能量转移而在近红外区域表现出敏化发射。通过瞬态吸收技术研究了能量转移，该技术深入了解了天线效应的动力学和效率。
