Mechanisms of Solvent‐Mediated Structural Transformations for Dynamic Crystals of Supramolecular Coordination Systems

Abstract

Thus far, reports about the transformations for dynamic crystals of supramolecular coordination systems mainly include single-crystal-to-single-crystal reactions, and solvent-mediated processes. This Concept focuses on the mechanisms for solvent-mediated structural transformations of dynamic crystals, which can be classified into two categories, that is, core-on-shell and core-to-core. The core-on-shell mechanism means that the core of the new crystal is generated from the shell of original crystal, being concomitant with the dissolution of the mother crystal. In contrast, for the core-to-core case, the growth of new crystal core and the dissolution of original crystal core will proceed simultaneously, but they are physically separated. Herein, the two mechanisms are elucidated in detail, with some typical examples from recent advances.

Ligand-driven self-assembly of iodine-based Cd(ii) complexes via dissolution–recrystallization structural transformation

“…The recrystallization of 1 to yellow-grey prism crystals of 4 started after 2 days, while the dissolution of 1 and the recrystallization of 2 occurred simultaneously due to a large difference in solubility between the initial 1 (more soluble) and the final 2 (less soluble) crystals in the methanolic solution of iodine. [39][40][41] The varied evidence in MeOH and MeCN suggests that solvents play a key role in the DRST process, which results in a different solubility of the starting complex and produces different chemically and thermodynamically stable products (Fig. 1).…”

Variations in the structural composition of pyrazole-3,5-dicarboxylato Cu(ii) complexes with 1,2-di(4-pyridyl)ethane synthesized under different conditions

“…9,10 It also plays an important role in the dissolution-recrystallization structural transformation in many complexes. 11,12 The Cu(II) center is one of the d 9 transition metal ions with a variety of coordination numbers and geometries with the Jahn-Teller distortion. 13,14 A versatile ligand, pyrazole-3,5-dicarboxylic acid (H 3 pzdc) is a multidentate ligand with six potential coordination sites including four carboxylate oxygen and two pyrazole nitrogen atoms.…”

Solvent-mediated structural transformations of copper(II) coordination polymers induced by different short-chain alcohols

“…A solvent can act as a very effective tool for stimulating the structural transformations of CPs (Zhou et al, 2018). Solvent normally acts as a guest or ligand to form interactions with the coordination motifs (Bloch & Sumby, 2012).…”