Stars and stripes: hexatopic tris(3,2':6',3"-terpyridine) ligands that unexpectedly form one-dimensional coordination polymers

The hexatopic ligands 1,3,5-tris(4,2':6',4''-terpyridin-4'-yl)benzene (1), 1,3,5-tris(3,2':6',3''-terpyridin-4'-yl)benzene (2), 1,3,5-tris[4-(4-(4,2':6',4''-terpyridyl)phenyl]benzene (3), 1,3,5-tris[4-(4'-3,2':6',3''-terpyridyl)phenyl]benzene (4) and 1,3,5-tris[4-(4'-3,2':6',3''-terpyridyl)phenyl]mesitylene (5) have been prepared and characterized. The single crystal structure of 1.1.75DMF was determined; 1 exhibits a...

Designing narcissistic self-sorting terpyridine moieties with high coordination selectivity for complex metallo-supramolecules

Coordination-driven self-assembly is a powerful approach for the construction of metallosupramolecules, but designing coordination moieties that can drive the self-assembly with high selectivity and specificity remains a challenge. Here we report two ortho-modified terpyridine ligands that form head-to-tail coordination complexes with Zn(II). Both complexes show narcissistic self-sorting behaviour. In addition, starting from these ligands, we obtain two sterically congested multitopic ligands and use them to construct more complex metallo-supramolecules hexagons. Because of the non-coaxial structural restrictions in the rotation of terpyridine moieties, these hexagonal macrocycles can hierarchically self-assemble into giant cyclic nanostructures via edge-to-edge stacking, rather than face-to-face stacking. Our design of dissymmetrical coordination moieties from congested coordination pairs show remarkable self-assembly selectivity and specificity.

Structural variations of trinitrato(terpyridine)lanthanoid complexes

The structural characterization of the newly synthesized trinitrato(terpyridine)lanthanoid complexes [Nd(NO3)3(pytpy)(H2O)] (1), [Eu(NO3)3(pytpy)(EtOH)]·EtOH (2·EtOH) and [Tb(NO3)3(ptpy)(EtOH)] (3), with the modified terpyridine ligands pytpy = 4′-(pyridin-3-yl)-2,2′:6′,2″-terpyridine and ptpy = 4′-phenyl-2,2′:6′,2″-terpyridine, show all a coordination number of 10 at the metal ion with three bidentate nitrato ligands and an additional solvent ligand. The coordination polyhedra around the metal ions are highly irregular. Hirshfeld surface analyses of the intermolecular interactions show (C/O–)H⋯O bonding having the largest percentage contribution in all three structures, while there are remarkably few π-π interactions despite the numerous aryl rings.

Designing Narcissistic Self-Sorting Terpyridine Moieties with High Coordination Selectivity for Complex Metallo-Supramolecules

Coordination-driven self-assembly serves as a powerful approach for the construction of metallo-supramolecules, however, it still remains its infancy in design of coordination moieties with high selectivity and specificity. Herein, two unique ortho-modified terpyridine ligands (MA and MB) were designed and synthesized to form head-to-tail coordination complexes with Zn(II) respectively. Both of them showed excellent narcissistic self-sorting process due to the exquisite design. Further, two multitopic ligands (LA and LB) with narcissistic self-sorting moieties were obtained and used to construct more complex metallo-supramolecules hexagons. More interestingly, because of the non-coaxial structural restrictions in the rotation of terpyridine moieties, the obtained hexagonal macrocycles were able to hierarchically self-assemble into giant cyclic nanostructures via side-to-side stacking rather than face-to-face stacking. Our design of dissymmetrical coordination moieties could pave a new avenue for the development of congested coordination pairs with high selectivity and specificity.

Isomers of Terpyridine as Ligands in Coordination Polymers and Networks Containing Zinc(II) and Cadmium(II)

The use of divergent 4,2’:6’,4”- and 3,2’:6’,3”-terpyridine ligands as linkers and/or nodes in extended coordination assemblies has gained in popularity over the last decade. However, there is also a range of coordination polymers which feature 2,2’:6’,2”-terpyridine metal-binding domains. Of the remaining 45 isomers of terpyridine, few have been utilized in extended coordination arrays. Here, we provide an overview of coordination polymers and networks containing isomers of terpyridine and either zinc(II) and cadmium(II). Although the motivation for investigations of many of these systems is their luminescent behavior, we have chosen to focus mainly on structural details, and we assess to what extent assemblies are reproducible. We also consider cases where there is structural evidence for competitive product formation. A point that emerges is the lack of systematic investigations.

Copper chloride complexes with substituted 4′-phenyl-terpyridine ligands: synthesis, characterization, antiproliferative activities and DNA interactions

Eleven copper chloride complexes (1–11) with 4′-(4′-substituted-phenyl)-2,2′:6′,2′′-terpyridine complexes bearing hydrogen (L1), cyano (L2), p-hydroxyl (L3), m-hydroxyl (L4), o-hydroxyl (L5), methoxyl (L6), iodo (L7), bromo (L8), chloro (L9), fluoro (L10) or...

Metal-Containing Monomers Based on Copper and Zinc Salts of Unsaturated Acids and Pendent 4-phenyl-2,2′:6′,2′′-terpyridine Ligands: Synthesis, Characterization and Thermal Properties

Metal-containing monomers based on maleates of copper and zinc, cinnamate of copper and acrylate of zinc with 4-phenyl-2,2′:6′,2′′-terpyridine ligand were prepared for the first time and characterized using a number of analytical techniques including infrared spectroscopy, elemental analysis and thermal gravimetric analysis. According to the results of the thermal analysis, the coordination mixed-ligand complexes based on zinc salts are more stable than copper one both in the case of monocarboxylic acids and dicarboxylic acids. The first stage of polymerization according to results of mass spectra of gaseous products is initiated in accordance with the Borodin–Hunsdiecker mechanism: the initial decarboxylation leads to the formation of carboxy biradicals, which, in turn, cause the polymerization and the formation of polymers. In this paper we also describe facile two-step Kröhnke-type synthesis of 4′-phenyl-2,2′:6′,2′′-terpyridine from 2-acetylpyridine and its NMR spectrum.