Department of Chemistry, University of California, Riverside, California 92521, United States.
Inorg Chem. 2011 Oct 3;50(19):9430-42. doi: 10.1021/ic201092s. Epub 2011 Sep 8.
A series of tetracationic M(2)L(4) palladium-pyridyl complexes with endohedral amine functionality have been synthesized. The complexes were analyzed by NMR techniques (including Diffusion NMR and 2D NOESY), electrospray ionization (ESI) mass spectrometry, and X-ray crystallography. The solid state analysis shows a large change in crystal morphology upon introduction of the endohedral amine groups, caused by deleterious interactions between the amines and the triflate counterions from the coordination process. Combination of different ligands allows analysis of ligand exchange rates via NMR analysis, with half-lives on the order of 3 h, independent of the donor properties of the ligand. Self-sorting behavior is observed, with more electron-rich ligands being favored. The amine-containing and extended complexes are strongly fluorescent, giving quantum yields of up to 83%.
一系列具有笼状胺官能团的内配位的四核 M(2)L(4)钯-吡啶配合物已被合成。通过 NMR 技术（包括扩散 NMR 和 2D NOESY）、电喷雾电离（ESI）质谱和 X 射线晶体学对配合物进行了分析。固态分析表明，引入笼状胺基团后，晶体形态发生了很大的变化，这是由于胺与配位过程中三氟甲磺酸根阴离子之间的有害相互作用所致。不同配体的组合允许通过 NMR 分析分析配体交换速率，半衰期约为 3 小时，与配体的给电子性质无关。观察到自分类行为，具有更多富电子配体的更有利。含胺和扩展的配合物具有很强的荧光，量子产率高达 83%。
