School of Chemistry and Trinity Biomedical Sciences Institute, Trinity College, Pearse St, Dublin 2, Ireland.
Dalton Trans. 2014 Jan 7;43(1):196-209. doi: 10.1039/c3dt52309h.
2,6-Bis(1,2,3-triazol-4-yl)pyridine (btp) is a terdentate binding motif that is synthesised modularly via the CuAAC reaction. Herein, we present the synthesis of ligands 1 and 2 and the investigation of the coordination chemistry, photophysical behaviour and electrochemistry of complexes of these with a number of d-metal ions (e.g. Ru(II), Ir(III), Ni(II) and Pt(II)). The X-ray crystal structures of ligand 1 and the complexes Ru·2(2)Cl, Ni·1(2)Cl and [Ir·1Cl3] are also presented. All of the complexes displayed non-classical triazolyl C-H···Cl(-) hydrogen bonding. All but one complex showed no metal-based luminescence at room temperature, while all of the Pt(ii) complexes displayed luminescence at 77 K. The electrochemistry of the Ru(II) complexes was also studied and these complexes were found to have higher oxidation potentials than analogous compounds. The redox behaviour of RuL2 complexes with both 1 and 2 was nearly identical, while [Ru·1Cl2(DMSO)] was oxidised at significantly lower potential. We also show that the Ru(II) complex of 2, Ru·2(2)Cl, gave rise to the formation of a metallo-supramolecular gel, the morphology of which was studied using scanning electron and helium ion microscopy.
2,6-双(1,2,3-三唑-4-基)吡啶(btp)是一种三齿配位基,可通过铜催化的叠氮-炔环加成(CuAAC)反应以模块化的方式合成。本文介绍了配体 1 和 2 的合成,并研究了这些配体与多种 d 金属离子(如 Ru(II)、Ir(III)、Ni(II)和 Pt(II))形成的配合物的配位化学、光物理行为和电化学性质。还介绍了配体 1 和配合物Ru·2(2)Cl、Ni·1(2)Cl 和[Ir·1Cl3]的 X 射线晶体结构。所有配合物均显示非经典三唑基 C-H···Cl(-)氢键。除一个配合物外,所有配合物在室温下均无金属基发光,而所有 Pt(ii)配合物在 77 K 时均显示发光。还研究了 Ru(II)配合物的电化学性质,发现这些配合物的氧化电位高于类似化合物。RuL2配合物与 1 和 2 的氧化还原行为几乎相同,而[Ru·1Cl2(DMSO)]则在明显较低的电位下被氧化。我们还表明,2 的 Ru(II)配合物Ru·2(2)Cl 导致形成金属超分子凝胶,使用扫描电子和氦离子显微镜研究了其形态。