The rational synthesis of (10,3)-type MOFs based on tetranuclear [W(Mo)OS3Cu3]+ secondary building units.

The self-assembly reaction of the preformed clusters with two extended linear and trigonal rigid ligands as organic linkers afforded two 2D and 3D Mo(W)/Cu/S-based cluster polymers. They show unprecedented structure types in Mo(W)/S/Cu chemistry and exhibit strong third-order nonlinear optical properties.