Narcissistic, Integrative, and Kinetic Self-Sorting within a System of Coordination Cages

Abstract

Many useful principles of self-assembly have been elucidated through studies of systems where multiple components combine to create a single structure. More complex systems, where multiple product structures self-assemble in parallel from a shared set of precursors, are also of great interest, as biological systems exhibit this behavior. The greater complexity of such systems leads to an increased likelihood that discrete species will not be formed, however. Here we show how the kinetics of self-assembly govern the formation of multiple metal−organic architectures from a mixture of five building blocks, preventing the formation of a discrete structure of intermediate size. By varying ligand symmetry, denticity, and orientation, we explore how five distinct polyhedraa tetrahedron, an octahedron, a cube, a cuboctahedron, and a triangular prismassemble in concert around Co II template ions. The underlying rules dictating the organization of assemblies into specific shapes are deciphered, explaining the formation of only three discrete entities when five could form in principle.

Exploiting host–guest chemistry to manipulate magnetic interactions in metallosupramolecular M4L6 tetrahedral cages

“…S1). (2)(3)(4)(5)(6)(7)(8) were obtained from vapour diffusion of THF and/or Et2O into the MeCN mother liquor. Synchrotron radiation was required to obtain single crystal data for complexes 2 (MX4 = MnCl4 2− ), 7 (MX4 = NiCl4 2− ) and 8 (MX4 = CuCl4 2− ).…”

“…Co II ) are employed, characterising magnetic properties has not been a key focus. 7,8 However, the exploitation of (reversible) guest encapsulation to induce magnetic exchange interactions with the host could be used in a variety of potential applications including magnetic sensing and switching, 9 the construction of single-molecule magnets, 10 the encapsulation and stabilisation of highly anisotropic single ion magnets with specific geometries, 11,12 dilution of magnetic molecules in the solidstate, 13 and the organisation of electron spin based qubits within ordered structural frameworks and/or on surfaces. 14,15 The latter has proven to be extremely difficult since the magnetic properties of molecules are often changed upon deposition.…”

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

“…[39][40][41] It has been more than twenty years since Lehn reported the first narcissistic self-sorting of a double helix, and there have also been many reports about narcissistic self-sorting in metal coordination. [42][43][44][45] However, most of these studies considering the narcissistic self-sorting of the structure as a whole, while the report focusing on narcissistic self-sorting used as self-recognition sites remains limited. [45][46][47][48][49][50] Furthermore, the homogeneous interactions in biological systems also prompted scientists to urgently develop ligand motifs for selfrecognition.…”

“…[42][43][44][45] However, most of these studies considering the narcissistic self-sorting of the structure as a whole, while the report focusing on narcissistic self-sorting used as self-recognition sites remains limited. [45][46][47][48][49][50] Furthermore, the homogeneous interactions in biological systems also prompted scientists to urgently develop ligand motifs for selfrecognition. [51][52] In this paper, to achieve coordination with high selectivity and specificity, we design two novel ortho-modified terpyridine ligands, i.e., MA and MB as model systems to form head-to-tail coordination complexes Zn 2 (MA) 2 and Zn 3 (MB) 2 , respectively (Scheme 1b).…”

A heterobimetallic tetrahedron from a linear platinum(II)-bis(acetylide) metalloligand

“…Increasing the structural complexity, however, usually implies growing synthetic efforts that have to be made to obtain the necessary organic ligands [15][16][17]. A great way to simplify ligand syntheses is the subcomponent self-assembly strategy [18][19][20][21][22][23]. Following this strategy, the actual ligand is generated in situ during the self-assembly process via reversible formation of covalent bonds, in most cases imine bonds.…”