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Control of polymeric structure is among the most important
endeavours of modern macromolecular science. In particular,
tailoring the positioning and strength of intermolecular forces
within macromolecules by synthetic me- odsandthusgaining
structuralcontrolover the?nalpolymeric materials has become
feasible, resulting in the ?eld of supramolecular polymer science.
- sides other intermolecular forces, hydrogen bonds are unique
intermolecular forces enabling the tuning of material properties
via self-assembly processes -1
overawiderangeofinteractionstrengthrangingfromseveralkJmol tosev-
-1 eraltensofkJmol .
Centralfortheformationofthesestructuresareprecursor molecules of
small molecular weight (usually lower than 10 000), which can
assembleinsolidorsolutiontoaggregatesofde?nedgeometry.
Intermolecular
hydrogenbondsatde?nedpositionsofthesebuildingblocksaswellastheir-
spectivestartinggeometryandtheinitialsizedeterminethemodeofassembly
into supramolecular polymers forming network-, rodlike-, ?brous-,
disclike- , helical-, lamellar- and chainlike architectures. In all
cases, weak to strong
hydrogen-bondinginteractionscanactasthecentralstructure-directingforce
fortheorganizationofpolymerchainsandthusthe?nalmaterials'properties.
Theimportantcontributionofhydrogenbondstotheareaofsupramole- lar
polymer chemistry is de?nitely outstanding, most of all since the
potency of hydrogen-bonding systems has been found to be unique in
relation to other supramolecular interactions. Thus the high level
of structural diversity of many hydrogen-bonding systems as well as
their high level of direction- ity and speci?city in
recognition-phenomena is unbeaten in supramolecular chemistry. The
realization, that their stability can be tuned over a wide range of
binding strength is important for tuning the resulting material
prop- ties, ranging from elastomeric to thermoplastic and even
highly crosslinked duroplastic structures and networks. On the
basis of the thermal reversib- ity, new materials with highly
tunable properties can now be prepared, - ing able to change their
mechanical and optoelectronic properties with very
smallchangesofexternalstimuli. Thusthe?eldofhydrogen-bondedpolymers
forms the basis for stimuli responsive and adaptable materials of
the future.
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