Fundamental entropic chain effects enable the tuning of modular ligation chemistry – for example dynamic Diels–Alder (DA) reactions in materials applications – not only classically <i>via</i> the chemistry of the applied reaction sites, but also <i>via</i> the physical and sterical properties of the molecules that are being joined. The lecture will discuss our findings that evidence a significant impact of not only chain mass and length with a difference in the degree of debonding of up to 30 % for different lengths of macromonomers of the same polymer type but – remarkably – also a chain stiffness effect with a difference in bonding degrees of nearly 20 % for isomers. Entropic chain effects govern every reversible ligation chemistry and indeed every cleavage reaction. The lecture will evidence these effects on several examples.

Entropy driven chain effects on ligation

249th National Meeting (2015)

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