Multitopic 3,2′:6′,3′′-terpyridine ligands as 4-connecting nodes in two-dimensional 4,4-networks

The tetratopic 1,4-bis(2-phenylethoxy)-2,5-bis(3,2′:6′,3′′-terpyridin-4′-yl)benzene (1) and 1,4-bis(3- phenylpropoxy)-2,5-bis(3,2′:6′,3′′-terpyridin-4′-yl)benzene (2) ligands have been prepared and fully characterised. Combination of ligand 1 or 2 and [M(hfacac)2]·xH2O (M = Cu, x = 1; M = Zn, x = 2) under conditions of crystal growth by layering led to the formation of [Cu2(hfacac)4(1)]n·3.6n(1,2-Cl2C6- H4)·2nCHCl3, [Zn2(hfacac)4(1)]n·nMeC6H5·1.8nCHCl3, [Cu2(hfacac)4(2)]n·nMeC6H5·2nH2O, [Cu2(hfacac)4(2)]n·2.8nC6H5Cl and [Cu2(hfacac)4(2)]n·2n(1,2-Cl2C6H4)·0.4nCHCl3·0.5nH2O. For each compound, single-crystal X-ray analysis revealed the assembly of a planar (4,4)-net in which the tetratopic ligands 1 or 2 define the nodes. The metal centres link two different bis(3,2′:6′,3′′-tpy) ligands via the outer pyridine rings; whereas copper(II) has N-donors in a trans-arrangement, zinc(II) has them in cis. This difference between the copper(II) and zinc(II) coordination polymers modifies the architecture of the assembly without changing the underlying (4,4)-network