Symmetry Driven Self-Assembly of Metallo-Supramolecular Architectures

Abstract

The self-assembly of well-defined metallosupramolecular aggregates highly depends on the symmetry of the ligands as well as of the metals. Approaches in which symmetry considerations allow the stepwise-''hierarchical''-assembly of helicate-type complexes from very simple catechol derivatives are described. In addition helicates and meso-helicates are stereoselectively obtained by the use of linear ligands possessing the relevant symmetry element for the formation of either diastereomer (even-odd principle). In case of helicates, this allows the preparation of enantiomerically pure complexes. Finally, the self-assembly of tetrahedral M 4 L 4 complexes is described using either constrained flexible or highly predisposed rigid ligands.

Influencing the Self‐Sorting Behavior of [2.2]Paracyclophane‐Based Ligands by Introducing Isostructural Binding Motifs

“…Although the formation of helical polymeric structures from discrete cyclic structures, as observed in case of [(dppp)Pd{( S p )‐ L iso }] n (OTf) 2 n and [(dppp)Pd{( R p )‐ L nit }] n (OTf) 2 n , is in accordance with earlier observations and other self‐assembled polymers, the formation of bowl‐shaped, concave, yet polymeric, structures as observed in [(dppp) 2 Pd 2 {( S p )‐ L nit }{( R p )‐ L nit }] n (OTf) 4 n , is more scarce, both on the level of discrete supramolecular structures as well as on the level of self‐assembled polymers.…”

Chiral biomolecule based dodecanuclear dysprosium(iii)–copper(ii) clusters: structural analyses and magnetic properties

“…[1][2][3][4][5][6] Among these, coordination architectures with excellent symmetric features have been the most investigated ones owing to their captivating coordination environments, giving rise to utilitarian attributes as a consequence of their symmetry-aided structure-property correlation. [7][8][9][10][11][12][13] The inherent symmetry in such complexes makes the structure-property correlation much easier to predict, leading to a strategic rationale based design principle for attaining the target properties and an insight thereinto. Over the decades, employment of a binary or ternary combination of linkers for yielding such complexes has proved quite an efficient protocol.…”

One‐Step Versus Multistep Equilibrium of Carbazole‐Bridged Dinuclear Zinc(II) Complex Formation: Metal‐Assisted π‐Association and ‐Dissociation Processes

“…In this work, these questions are addressed by investigating metal-assisted p-association and -dissociation processes in one step versus multistep formation of carbazole-bridged dinuclear complexes. [24][25][26][27][28][29][30] The carbazole ligand (L) forms a 4:2 complex [(L) 4 À(Zn 2+ ) 2 ] at a molar ratio of zinc ions (Zn 2 + ) to the ligand of 0.50, [31][32][33] which provides the opportunity for p stacking between the carbazole ligands. In the multistep mechanism, the 4:2 complex undergoes a structural transition to a 3:2 complex [(L) 3 À(Zn 2+ ) 2 ] at the higher molar ratio, thereby resulting in dissociation of p stacking between the carbazole ligands.…”