Superstructural diversity in two dimensions: crystal engineering of laminated solids

Abstract

The application of supramolecular concepts such as selfassembly to the solid state offers an approach to crystal design and crystal engineering, namely supramolecular synthesis of solids, that is based upon the design of infinite networks. Selfassembly of more than one molecular component, modular selfassembly, is particularly attractive since it can be accomplished in one-pot reactions with existing molecular components and allows for facile fine-tuning of structural and functional features. The challenges and opportunities that face crystal engineering are illustrated by concentrating on the superstructural diversity that has been exhibited in 2D network structures. Despite the observed superstructural diversity, which can manifest itself in the form of supramolecular isomerism, and the range of molecular components that have been utilized, these structures have in common an inherent ability to mimic clays by intercalation of guest molecules.

Two different one-dimensional structural motifs in the same coordination polymer: a novel interpenetration of infinite ladders by bundles of infinite chains

“…[1][2][3] Product topology can often be influenced by selecting the coordination geometry of the metals and the chemical nature of the organic ligands. In particular, the T-joint building block, defined by the coordination of a metal center by three N,NA-bidentate ligands, has given rise to several isomeric framework types via different orientation of the T-joints relative to one another.…”

“…[4][5][6] While different structural isomers can form from T-shaped building blocks, and while it is not unusual to find multiple structural isomers within the same batch of crystals, 4,7 it is quite rare to find two structural motifs within the same crystal structure. [8][9][10][11] The use of the long ligand 1,4-bis[(4A-pyridylethynyl)benzene] (1) 12 has led to the formation of a highly unusual interpenetrated network in [Cu (1) The one-dimensional ladders are composed of T-shaped building blocks with the copper center in a five-coordinate trigonal bipyramidal environment (Fig. 1a) consisting of three pyridyl nitrogen donors (two axial and one equatorial), one from each of the three ligands, 1, and two equatorial oxygen donors from two monodentate nitrate ions.…”

Crystal structure of poly[1,2-bis(1,2,4-triazol-4-yl)ethane-κ2 N:N′]silver(I) bromate monohydrate]silver(I), C6H10AgBrN6O4

“…A successful strategy for construction of such networks is to employ appropriate ligands that can bond metal ions in different modes and provide a way to obtain new materials with intriguing architectures and excellent physical properties [4][5][6][7]. Many factors such as the coordination geometry of the central atom, the structural characteristics of the ligands, the solvent system, and the counterions can play key roles in the construction of the coordination networks.…”

A Topology Paradigm for Metal‐Organic Zeolites

“…[5] Attractive metal-organic-zeolite models of metal-organic frameworks may be predicted for novel "2D building blocks" of semiregular topology [6] (Figure 1 b and c) that are expanded in a third direction by pillaring. [7] In this case, initial plane tiling by a set of different polygons, instead of uniform square grids as in [Cu(bipy) 2 SiF 6 ], [2] generates closely packed molecular triangles (cf. molecular hexagons) with very open regions within the network.…”