One-pot conditional self-assembly of multicopper metallacycles

The self-assembly of supramolecular metallacycles via the coordination-driven directional bonding approach can be modified to produce some unexpected structural variations. The combination of a flexible ligand-capped dinuclear transition-metal acceptor like [Cu(2)(dppm)(2)(NCMe)(2)]X(2) (1X(2); dppm = Ph(2)PCH(2)PPh(2); X(-) = BF(4)(-), PF(6)(-), or BPh(4)(-)) with monodentate-bidentate donors like 2-, 3-, and 4-pyridylcarboxylates produced oligomeric compounds [{Cu(2)(dppm)(2)}(μ-(2-PyCO(2)))](2)X(2) (2X(2)), [{Cu(2)(dppm)(2)}(μ-(3-PyCO(2)))](2)X(2) (3X(2)), and [{Cu(2)(dppm)(2)}(μ-(4-PyCO(2)))](4)X(4) (4X(4)), respectively, as the thermodynamically stable products in one-pot reactions. However, the modified self-assembly is still subject to steric hindrance. The reaction of complex 1(BF(4))(2) with 6-Me-3-PyCO(2)H did not produce a polygonal dimeric metallacycle but a simple dinuclear complex, [Cu(2)(dppm)(2)(6-Me-3-PyCO(2))](BF(4)) (5(BF(4))). The crystal structures of complexes 2(PF(6))(2), 3(PF(6))(2), 4(BF(4))(4), and 5(BF(4)) were determined using X-ray diffraction.