The Cu(I)-catalyzed 1,3-cycloaddition of organic azides with terminal alkynes, the CuAAC "click" reaction is currently receiving considerable attention as a mild, modular method for the generation of functionalized ligand scaffolds. Herein we show that mild one-pot "click" methods can be used to readily and rapidly synthesize a family of functionalized bidentate 2-pyridyl-1,2,3-triazole ligands, containing electrochemically, photochemically, and biologically active functional groups in good to excellent yields (47-94%). The new ligands have been fully characterized by elemental analysis, HR-ESI-MS, IR, (1)H and (13)C NMR and in three cases by X-ray crystallography. Furthermore we have demonstrated that this family of functionalized "click" ligands readily form bis-bidentate Pd(II) complexes. Solution studies, X-ray crystallography, and density functional theory (DFT) calculations indicate that the Pd(II) complexes formed with the 2-(1-R-1H-1,2,3-triazol-4-yl)pyridine series of ligands are more stable than those formed with the [4-R-1H-1,2,3-triazol-1-yl)methyl]pyridine "click" ligands.
Two mononuclear Dy III crown ether complexes [Dy(15C5)(H 2 O) 4 ](ClO 4 ) 3 Á(15C5)ÁH 2 O (1) and [Dy(12C4)(H 2 O) 5 ](ClO 4 ) 3 ÁH 2 O (2) have been prepared and characterized. X-ray diffraction studies show that both compounds crystallize as half sandwich type structures with muffin and pseudo-capped square antiprismatic geometries respectively. Despite the comparable local environments of the Dy III ions they display remarkably different dynamic magnetic properties with only 1 displaying SMM properties in zero field. The solid state emission spectra for both 1 and 2 display sharp bands associated with f-f transitions.From the fine structure of the 4 F 9/2 -6 H 15/2 band, the Stark splitting of the 6 H 15/2 ground state permitted the energy difference between the ground and first excited state to be determined. For 1 this value (DE = 58.0 AE 3.0 cm À1 ) is in excellent agreement with ab initio calculations and the experimentally observed SMM behaviour. For 2, the photoluminescence data and theoretical calculations support a less well isolated ground state (DE = 30 AE 3.0 cm À1 ) in which a rapid relaxation process affords no SMM behaviour in zero-field.
Readily synthesised and functionalised di-1,4-substituted-1,2,3-triazole "click" ligands are shown to self-assemble into coordinatively saturated, quadruply stranded helicate molecular cages with Pd(II) ions.
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