Coordination chemistry of heterocycle-functionalized diazamesocycles: tuning the productive NiII complexes through altering the pendants of ligands

In order to further understand the coordination chemistry of diazamesocyclic systems, a series of mononuclear NiII complexes with 1,4-diazacycloheptane (DACH) functionalized by additional imidazole or pyridine donor pendants, including [NiL1](ClO4)2 · H2O (1), [NiL1Cl](ClO4) (2), [NiL2Cl](ClO4) · CH3OH (3), [NiL2Cl][NiL2](ClO4)3 (4) and [NiL3](ClO4)2 (5), where L1 = 1,4-bis(N-1-methylimidazol-2-yl-methyl)-1,4-diazacycloheptane, L2 = 1,4-bis(pyridyl-2-yl-methyl)-1,4-diazacycloheptane, and L3 = 1,4-bis-(imidazol-4-yl-methyl)-1,4-diazacycloheptane, have been prepared and characterized. A detailed study on the solid structures and solution spectra of these complexes indicates that tetradentate ligands L1, L2 and L3 would lead to new NiII complexes with different coordination environments in the solid states and solution. The N-methyl substituted imidazole functionalized ligand L1 forms green compound 2 and yellow product 1; while the pyridine functionalized ligand L2 affords red product 4 and green complex 3; the ligand L3 results in only one stable mononuclear NiII product 5. The solution behaviors of these interesting compounds were also investigated by UV–Vis technique.

Graphical abstractIn order to further understand the coordination chemistry of diazamesocyclic systems, a series of NiII complexes with 1,4-diazacycloheptane (DACH) functionalized by additional imidazole or pyridine donor pendants, have been prepared and structurally characterized.Figure optionsDownload full-size imageDownload as PowerPoint slide