Multicomponent Self‐Assembly: Spontaneous Formation of a Cylindrical Complex from Five Ligands and Six Metal Ions

Abstract

Self-assembly consists of the spontaneous generation of a well-defined. discrete supramolecular architecture from a given set of components under specific conditions. Such processes require the design of "programmed" supramolecular systems that rely on the information stored in the components and on the interaction algorithm that operates through molecular recognition events.". 21 Depending on the nature of the molecules involved, the self-assembly can be organic o r inorganic. In the assembly of supermolecules from metal ions and ligands, the latter must contain the steric program that is "read" by the metal ions following the algorithm represented by their coordination geometry. The selfassembly of a given superstructure involves three stages : recognition between the components, correct orientation so as to allow growth, and termination of the process leading to a discrete, finite supramolecular species." -31The formation of double-helical metal complexes, the helicates,[, results from the self-organization of oligobipyridine (bpy) strands and Cu' o r Ag' ions that possess tetrahedral coordination ge0metry.1~ -51 The interaction of appropriately substituted oligo-bpy strands or related ligands with metal ions prefering octahedral coordination may yield triple-helical complexes.['* 81 Closed inorganic structures have been obtained, for instance, from the self-assembly of Ni2+[9d1 or C U * + [~~] ions and bis-p-diketone type ligands, of four Pt" metal complex fragments and four 4,4bpy groups,"'' and of four C u + ions and four bispyridylpyridazine ligands." 'I The self-assembly of the helicates and related structures involves just one type of ligand and metal ion. Further progress in the understanding and the control of the self-assembly and self-organization of inorganic (as well as of purely organic) superstructures requires the conception of systems

Solvent-dependent Assembly of Discrete and Continuous CoCl2 Adamantane-based Ligand Complexes: Observations by CSI–Mass Spectrometry and X-ray Crystallography

“…In structure control, it is important to adjust the metal-ligand stoichiometry based on the number of coordination sites or the coordination environment. For example, Lehn and coworkers 40 demonstrated the spontaneous formation of a cylindrical complex from five ligands and six metal ions, in which two hexaazatriphenylene derivatives acting as the planar molecule and three bisbipyridyl ligands linked at the 5,5′ positions acting as the pillar molecule were connected by three copper ions. The structure was characterized by 1 H NMR spectroscopy, fast atom bombardment mass spectrometry (MS), and single-crystal X-ray structure analysis.…”

Self-recognition in helicate self-assembly: spontaneous formation of helical metal complexes from mixtures of ligands and metal ions.

“…1 and 2), self-recognition allows the generation of the desired products from a mixture of starting compounds. These selfrecognition processes as well as the recently described multicomponent self-assembly of a cylindrical molecular cage (13) involve the interplay of three structural factors and two thermodynamic factors. The three structural factors are (i) structural features of the ligands (nature, number, and arrangement of the binding subunits and the nature and position of the spacers), (ii) the coordination geometries of the metal ions, and (iii) the steric and conformational effects within the different species resulting from the various possible combinations of ligands and metal ions in a given mixture.…”

Self-Organization of Nitrogen-Containing Polymeric Supramolecules in Thin Films

“…Supramolecular structures of pyridine oligomers [10] or their polymeric modifications [11] have typically been based on coordination. Covalent bonding has been used to produce polypyridine-based hairy rods [12] and internal hydrogen bonding [13] to planarize the rings.…”