An Alternate [2×2] Grid Constructed Around TiO4N2 Units

The formation of a tetranuclear self-assembled species constructed around a TiO₄N₂ motif is reported. This aggregate is generated from Ti(OⁱPr)₄, 2,2’-bipyrimidine (bpym) and a bis-biphenol strand (L²H₄) where two 2,2’-biphenol units are connected with a biphenyl spacer. The solid-state structure of the Ti₄(L²)₄(bpym)₄] architecture reveals the formation of an unprecedented chiral alternate 2×2] grid. In addition to the structural characterization of the Ti₄(L²)₄(bpym)₄] architecture, geometry optimisation on various possible isomeric tetrameric assemblies (2×2] grid, alternate 2×2] grid, circular helicate or cyclic hemihelicate) is performed using DFT calculations. These results confirm the higher stability of the alternate 2×2] grid over the other possible tetranuclear isomers and allow examining the replacement of the bpym ligands by two novel diimine chelates within the tetranuclear assembly (2,2’-bipyridine=bipy and 2,2’-bipyrazine=bipyraz). From this initial theoretical investigation, the competition between these three nitrogen ligands in the course of the self-assembly process is next evaluated. Overall, this investigation shows that the exclusive formation of the alternate 2×2] grid is driven by CH⋅⋅⋅N interactions.