Molecular and supramolecular recognition patterns in ternary copper(II) or zinc(II) complexes with selected rigid-planar chelators and a synthetic adenine-nucleoside.

Four ternary metal-complexes with Cu(II) or Zn(II), 2,6-pyridine-dicarboxylate (pdc) or glycyl-glycinate (GG) and the synthetic nucleoside 9-(2-hydroxyethyl)adenine (9heade) have been synthesized and studied by single-crystal X-ray diffraction and other physical methods. Relevant supramolecular assemblies found in the solid state structures have been further studied using density functional theory (DFT) calculations. In addition, the energetic features of the non-covalent interactions as well as the cooperativity effects have been calculated and characterized using the non-covalent interaction plot computational tool. Compounds trans -[Cu(pdc)(9heade)(H 2 O) 2 ·3H 2 O (1a) and [Cu(pdc)(9heade)(H 2 O)]·H 2 O (1b), trans -[Zn(pdc)(9heade)(H 2 O) 2 (2), share the same molecular recognition pattern consisting in the cooperation of the metal-N7(9heade) bond and an interligand (9heade)N6-H···O(pdc) interaction, regardless of the nature of the metal, the coordination environment and the water content. At a supramolecular level, these compounds exhibit pairs of complex molecules linked by H-bonds and interesting anion–π/π–π/π–anion assemblies (in 1a and 1b) or the unprecedented π-π interactions (in 2), involving the purine moieties or the exocyclic –6NH 2 purine groups, respectively. Compound 3 , {[Cu(GG)(9heade)(H 2 O)·Cu(GG)(μ 2 -9heade)]·8H 2 O} n , consists in asymmetric dinuclear complex units (Cu···Cu 7.83 Å) that connect with adjacent ones by pairs of very weak Cu-O(carboxylate) bonds (Cu···Cu 3.81 Å) building a polymeric chain. The supramolecular transition from a single molecule to dinuclear units and finally a polymeric chain is also observed in the electron paramagnetic resonance spectra and discussed from a structural point of view as well as by DFT calculations. The unprecedented N7 and μ-N7,O(ol) metal binding patterns of 9heade differs from that recently reported (μ-N1,N7) in a Cd(II) polymer. The molecular and supra-molecular recognition patterns in four Cu(II) or Zn(II) ternary complexes with two rigid-planar tridentate chelators and the nucleoside 9-(2-hydroxyethyl)adenine are discussed on the basis of crystallographic results and density functional theory calculations, providing a thorough evaluation of the contribution of interligand interactions. Unlabelled Image • Ternary complexes are studied by crystallographic and theoretical methods. • Rigid-planar tridentate chelators and an adenine synthetic nucleoside are involved. • The Zn(II) compound exhibits an unprecedented anti-parallel C···NH 2 π-interaction. • Interesting anti-parallel π-C·NH 2 or anion–π/π–π/π–anion interactions are reported. • The Cu-glycylglycinate-nucleoside forms dinuclear molecules that lead to a polymer. [ABSTRACT FROM AUTHOR]