Constitutional Self-Selection of [2 × 2] Homonuclear Grids from a Dynamic Mixture of Copper(I) and Silver(I) Metal Complexes

Abstract

This paper describes the controlled self-selection and quantitative parallel amplification of the homonuclear grid architectures derived from the same ligand 1 of different conformational geometries and Cu+ and Ag+ metal ions of different coordination behavior and ionic size.

Engineering Solid‐State Molecular Switches: N‐Salicylidene N‐Heterocycle Derivatives

“…[13] This diversity of interactions explains the complexity of supramolecules which can be either artificial (nanogrids, [14][15][16] nanoracks, [17] nanocages [18] ) or natural [19] (DNA, recognition proteins). Supramolecular interactions can be very stable (thermodynamic) or very labile (kinetic), [20] which allows the system to (re)organize either itself [21] or under a given constraint (temperature, [21] light irradiation, [10,22] pH [23] and solvent change, [21] concentration [21] ) to form complex self-assemblies.…”

Self-assembly of a M4L6 complex with unexpected S4 symmetry

“…However, after addition of one equivalent of Cu(I), which prefers tetrahedral coordination, an already known M 4 L 4 grid (C1) forms quantitatively. 15 While previously L2 was first synthesized and converted to C1 upon complexation with Cu(I), we have used subcomponent self-assembly approach to drive the mixture of 1, 2 and Cu(I) ions to C1 (2D grid, Fig. 1 Interestingly, C2 can be seen as the smallest supramolecular M 4 L 6 complex of its type reported to this date, possessing no internal cavity.…”

New [2 × 2] cyclic framework that induces distortions from square planar to tetrahedral around the copper(II) centers

“…That is, this framework inhibits square planar coordination geometries and imposes tetrahedral distortions for the metal centers because of the steric demands. Unique rectangular coordination frameworks have been achieved by tetrahedral copper(I) [1,2,5], silver(I) [5,8,9], and zinc(II) [4,6,7] ions.Synthesis of the copper(II) complexes with tetrahedrally distorted geometries has attracted intense attention not only for providing models of active sites of metalloenzymes [12][13][14][15], but also as fundamental studies of copper(II) coordination chemistry [16]. This is because the construction of a [2 · 2] cyclic framework by the copper(II) ions is a unique subject toward the synthesis of new copper(II) complexes with distorted coordination centers [15,17].…”

“…The self-assembled construction of the [2 · 2] cyclic framework illustrated in Scheme 1 by four bis-didentate rod-type ligands and four metal ions is one of the principal targets of supramolecular architectural synthesis [1][2][3][4][5][6][7][8][9][10][11]. This structure is interesting in that the cyclic framework regulates the geometries of the metal ions.…”

“…That is, this framework inhibits square planar coordination geometries and imposes tetrahedral distortions for the metal centers because of the steric demands. Unique rectangular coordination frameworks have been achieved by tetrahedral copper(I) [1,2,5], silver(I) [5,8,9], and zinc(II) [4,6,7] ions.…”