Directing metallo-supramolecular assembly through complementarity

Abstract

In chemistry, function and behaviour flow directly from structure. As chemists seek to develop highly complex functional molecules, we need to harness routes to complex structures. In metallosupramolecular self-assembly, this...

A pair of conjoined trinuclear sub-frameworks in a pentanuclear double-cavity discrete coordination cage

“…Diverging coordination vectors and appropriate bend angles of the ligands are important parameters that decide the nuclearity of the ensuing cages. Preparation of Pd(II)-based low-symmetry SCDCC has been achieved by either mixing of Pd(II) with a designer unsymmetrical ligand 14,[16][17][18][19][20][21] to afford orientational selectivity of ligand components, or mixing of Pd(II) with more than one type of ligand 14,[22][23][24][25][26] targeting mixed ligated integrative self-sorting.…”

A Reduced-Symmetry Pd2L4 Cage from a Heterotopic Dipyridyl Ligand

“…12 Complex self-assembly regimes are reliant on both enthalpic and entropic considerations, 13 and therefore complementarity between the components, including reinforc-ing supramolecular interactions beyond metal−ligand coordination, are key. 14,15 Labile metal−ligand coordination means that both concentration and/or stoichiometry can play roles in the solution speciation. 16,17 The stability of Pd-based species is also important for application and depends largely on ligand basicity.…”

Structural Flexibility of Metal Chelate Complexes and Its Relation to Supramolecular Chemistry

“…[18] Algar and Preston reviewed strategies for the assembly of less symmetrical supramolecular structures by using shape-complementary ligands. [19] However, all of these studies involve pyridine-based ligands, generally binding to metals such as Pd and Pt. In contrast, the present work compares the flexibility of different ligands as they bind to a variety of metals in several simple coordination geometries.…”

“…Reek and coworkers calculated the geometry of M m L n species through molecular dynamics, finding only small differences in the N−Pd−N angles among Pd 3 L 3 , Pd 4 L 4 , and Pd 2 L 3 [18] . Algar and Preston reviewed strategies for the assembly of less symmetrical supramolecular structures by using shape‐complementary ligands [19] . However, all of these studies involve pyridine‐based ligands, generally binding to metals such as Pd and Pt.…”