Supramolecular interactions in the solid state

Abstract

In the last few decades, supramolecular chemistry has been at the forefront of chemical research, with the aim of understanding chemistry beyond the covalent bond. Since the long-range periodicity in crystals is a product of the directionally specific short-range intermolecular interactions that are responsible for molecular assembly, analysis of crystalline solids provides a primary means to investigate intermolecular interactions and recognition phenomena. This article discusses some areas of contemporary research involving supramolecular interactions in the solid state. The topics covered are: (1) an overview and historical review of halogen bonding; (2) exploring non-ambient conditions to investigate intermolecular interactions in crystals; (3) the role of intermolecular interactions in morphotropy, being the link between isostructurality and polymorphism; (4) strategic realisation of kinetic coordination polymers by exploiting multi-interactive linker molecules. The discussion touches upon many of the prerequisites for controlled preparation and characterization of crystalline materials.

The staple role of hydrogen and halogen bonds in crystalline (E)-8-((2,3-diiodo-4-(quinolin-8-ylthio)but-2-en-1-yl)thio)quinolin-1-ium triiodide

“…Parallel chains of triiodide anions complement the cation chains; each terminal I(3) atom in the triiodide anion forms halogen bonds with the I(1) atom in the cation C-IÁÁÁI 3 -. Thus, the triiodide anion plays the staple role in binding cations into one chain, as if a side bracket (Fig.…”

“…The design of new materials, including that of crystal structures, requires the efficient control of supramolecular aggregation [1][2][3]. The structural organization of oligo-and poly-iodides of iodine-containing N-, S-heterocycles is very complicated.…”

Different molecular assemblies in two new phosphoric triamides with the same C(O)NHP(O)(NH)2 skeleton: crystallographic study and Hirshfeld surface analysis

“…The engineering of molecular crystals as well as the construction of supramolecular assemblies are both concerned with intermolecular interactions and hence are conceptually connected (Braga and Grepioni 1997). There is no doubt that the intermolecular contacts, especially hydrogen bonds, play a fundamental role in crystal engineering and stabilization of crystalline solids (Prins et al 2001;Steiner 2002;Metrangolo and Resnati 2008) and thus it is crucial to distinguish different types of interactions in any design strategy (Resnati et al 2015).…”

“…Supramolecular chemistry is a highly interdisciplinary field of science that has brought together investigators from many disciplines including chemistry, physics and biology (Desiraju 2010; Resnati et al 2015). The engineering of molecular crystals as well as the construction of supramolecular assemblies are both concerned with intermolecular interactions and hence are conceptually connected (Braga and Grepioni 1997).…”

Investigating the Structure Directing Properties of Designer 1,8-Naphthalimide and Amphiphilic Sulfonate Anions and Their FeIII Thiosemicarbazone Complexes

“…[1][2][3][4][5][6] The preparation of such supramolecular materials often relies on controlling and understanding weak intermolecular interactions in both the solution and the solid states. [7][8][9][10] Introducing functional groups into a system that have particular structure directing properties is one method that researchers have been using to control the overall architecture and topology of functional systems. Such "directed assembly" allows for functional metal complexes to be organised into macroscopic materials (e.g.…”