Can 2‑Pyridyl-1,2,3-triazole “Click” Ligands be Used to Develop Cu(I)/Cu(II) Molecular Switches?

Molecular switching processes are important in a range of areas including the development of molecular machines. While there are numerous organic switching systems available, there are far less examples that exploit inorganic materials. The most common inorganic switching system remains the copper­(I)/copper­(II) switch developed by Sauvage and co-workers over 20 years ago. Herein, we examine if bidentate 2-(1-benzyl-1H-1,2,3-triazol-4-yl)­pyridine (pytri) and tridentate 2,6-bis­[(4-phenyl-1H-1,2,3-triazol-1-yl)­methyl]­pyridine (tripy) moieties can be used to replace the more commonly exploited polypyridyl ligands 2,2′-bypyridine (bpy)/1,10-phenanthroline (phen) and 2,2′;6′,2″-terpyridine (terpy) in a copper­(I)/(II) switching system. Two new ditopic ligands that feature bidentate (pytri, L1 or bpytri, L2) and tridentate tripy metal binding pockets were synthesized and used to generate a family of heteroleptic copper­(I) and copper­(II) 6,6′-dimesityl-2,2′-bipyridine (diMesbpy) complexes. Additionally, we synthesized a series of model copper­(I) and copper­(II) diMesbpy complexes. A combination of techniques including nuclear magnetic resonance (NMR) and UV–vis spectroscopies, high-resolution electrospray ionization mass spectrometry, and X-ray crystallography was used to examine the behavior of the compounds. It was found that L1 and L2 formed [(diMesbpy)­Cu­(L1 or L2)]²⁺ complexes where the copper­(II) diMesbpy unit was coordinated exclusively in the tridenate tripy binding site. However, when the ligands (L1 and L2) were complexed with copper­(I) diMesbpy units, a complex mixture was obtained. NMR and MS data indicated that a 1:1 stoichiometry of [Cu­(diMesbpy)]⁺ and either L1 or L2 generated three complexes in solution, the dimetallic [(diMesbpy)₂Cu₂(L1 or L2)]²⁺ and the monometallic [(diMesbpy)­Cu­(L1 or L2)]⁺ isomers where the [Cu­(diMesbpy)]⁺ unit is coordinated to either the bidentate or tridentate tripy binding sites of the ditopic ligands. The dimetallic [(diMesbpy)₂Cu₂(L1 or L2)]­(PF₆)₂ complexes were structurally characterized using X-ray crystallography. Both complexes feature a [Cu­(diMesbpy)]⁺ coordinated to the bidentate (pytri or bpytri) pocket of the ditopic ligands (L1 or L2), as expected. They also feature a second [Cu­(diMesbpy)]⁺ coordinated to the nominally tridentate tripy binding site in a four-coordinate hypodentate κ²-fashion. Competition experiments with model complexes showed that the binding strength of the bidentate pytri is similar to that of the κ²-tripy ligand, leading to the lack of selectivity. The results suggest that the pytri/tripy and bpytri/tripy ligand pairs cannot be used as replacements for the more common bpy/phen-terpy partners due to the lack of selectivity in the copper­(I) state.