Abstract
Five coordination polymers formed from combinations of copper(II) acetate and 4′-(4-alkyloxyphenyl)-3,2′:6′,3″-terpyridines with methoxy (1), n-butoxy (2), n-pentyloxy (3) and n-heptyloxy (4) substituents are reported. Reaction of 1 with Cu(OAc)2∙H2O leads to the 1D-polymer [Cu2(μ-OAc)4(1)]n in which {Cu2(μ-OAc)4} paddle-wheel units are connected by ligands 1, or [{Cu4(μ3-OH)2(μ-OAc)2(μ3-OAc)2(AcO-κO)2(1)2}·2MeOH]n in which centrosymmetric tetranuclear clusters link pairs of ligands 1 to give a double-stranded 1D-polymer. Layering solutions of Cu(OAc)2∙H2O (in MeOH) over 2, 3 or 4 (in CHCl3) leads to the assembly of the 1D-polymers [2{Cu2(μ-OAc)4(2)}·1.25MeOH]n, [Cu2(μ-OAc)4(3)]n and [{Cu2(μ-OAc)4(4)}·0.2CHCl3]n. In all compounds, the 3,2′:6′,3″-tpy unit coordinates only through the outer pyridine rings, but the conformation of the 3,2′:6′,3″-tpy responds to changes in the length of the alkyloxy tails leading to changes in the conformation of the polymer backbone and in the packing of the chains in the crystal lattice in the chains featuring {Cu2(μ-OAc)4} paddle-wheel linkers.
Highlights
The directional assembly of coordination polymers and networks depends upon the compatibility of directing-nodes and linkers [1]
The results indicate that, on a preparative scale, ligand 1 reacts with Cu(OAc)2.H2O to immediately yield the 1D-coordination polymer [Cu2(μ-OAc)4(1)]n
{[Cu4 (μ3 -OH)2 (μ-OAc)2 (μ3 -OAc)2 (AcO-κO)2 (1)2 ]·2MeOH}n. This 1D coordination polymer crystallizes in the monoclinic space group C2/c and consists of ligands 1 linked by tetranuclear copper clusters
Summary
The directional assembly of coordination polymers and networks depends upon the compatibility of directing-nodes and linkers [1]. The manner in which the M2 (μ-O2 CR) units are connected in a coordination network depends upon the nature of the linkers, and whether the R group in the bridging carboxylate is coordinatively innocent or not. In a simple case, where R is non-coordinating, and the organic linker is a rigid rod, such as 4,40 -bipyridine (4,40 -bpy), a topologically and structurally linear 1D-chain is assembled, as for example in [Mo2 (μ-O2 Ct Bu) (4,40 -bpy)]n [6]. 3D-frameworks can be achieved by retaining a rigid linker, such as 4,40 -bpy, but introducing paddle-wheel units which incorporate multifunctional. Paddle-wheel motifs inOnce combination rigid bidentate linkers isassembly an established strategy for MOF for MOF[8,9] In a simple case, where R is non-coordinating, and the organic linker is a rigid rod, such as 4,40 -bipyridine (4,40 -bpy), a topologically and structurally linear 1D-chain is assembled, as for example in [Mo2 (μ-O2 Ct Bu) (4,40 -bpy)]n [6]. 3D-frameworks can be achieved by retaining a rigid linker, such as 4,40 -bpy, but introducing paddle-wheel units which incorporate multifunctional
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