Kinetic and Thermodynamic Control in Dynamic Covalent Synthesis

High performance poly(methyl methacrylate) via hindered urea bond crosslinking

“…19 (2) The selection of a dynamic covalent bond with suitable thermodynamic and kinetic properties at different temperatures is critical to ensure stability and reprocessibility of the products. 20 (3) It should be guaranteed that the embedment of DCBs does not compromise the original characteristics and functionality of materials.…”

Entropy directs the self-assembly of supramolecular palladium coordination macrocycles and cages

“…5 Realization of the origin and effect of these thermodynamic contributions enables rational improvement of the self-assembly of highly-ordered constructs used broadly in supramolecular chemistry, including coordination cages, metal-organic frameworks, and dynamic-covalent based constructs. 52,[59][60][61][62] In this report, we demonstrate that the self-assembly of an equimolar mixture of M and lin L in deuterated dimethyl sulfoxide (DMSO) affords a mixture of triangular (M 3 lin L 3 ) and square (M 4 lin L 4 ), and oligomeric (M n lin L n+1 ) assemblies as depicted in Scheme 1. 1,6 We employed variable temperature 1 H-NMR (VT-NMR) to determine the DH and DS of both oligomeric and macrocyclic assemblies, providing unprecedented thermodynamic insights into the self-assembly process.…”

“…5 Realization of the origin and effect of these thermodynamic contributions enables rational improvement of the self-assembly of highly-ordered constructs used broadly in supramolecular chemistry, including coordination cages, metal–organic frameworks, and dynamic-covalent based constructs. 52,59–62…”

Quantification and Prediction of Imine Formation Kinetics in Aqueous Solution by Microfluidic NMR Spectroscopy

“…The most frequently used dynamic bond is imine, which can be formed by condensation between aldehydes and amines under mild reaction conditions [3] . Precise control over both thermodynamics and kinetics of imine formation has greatly promoted the construction of complex structures and chemical systems [3b] . For instance, Cooper et al.…”