they consist of chains resulting from the polyassociation of covalent monomers
linked through non-covalent interactions. But, now peace reigns and coexistence is
thriving for the mutual fertilization of the molecular and supramolecular chemistry
of polymeric entities, with active cross-talk between the two areas [22–32].
The topics covered in the present text will be limited to some aspects of the more
recent developments that have emerged from supramolecular chemistry and have been
carried over to polymer chemistry. They concern the implementation of a basic feature
of supramolecular chemistry, its dynamic character. Indeed, novel perspectives are
opened if one considers that supramolecular chemistry is intrinsically a dynamic
chemistry in view of the lability of the interactions connecting the molecular components of a supramolecular entity and its resulting ability to incorporate, decorporate,
and exchange its molecular components. It is thus a dynamic non-covalent chemistry
(DNCC). This dynamic character may be imported into molecular chemistry by
introducing into molecular entities covalent bonds that may form and break reversibly,
so as to allow for a continuous change in the covalent constitution by reorganization
and exchange of building blocks, . The resulting dynamic covalent chemistry (DCC)
has developed extensively in recent years [33–41]. DNCC and DCC have been brought
together under the unifying concept of constitutional dynamic chemistry (CDC)
[41–43] covering both the molecular and supramolecular areas. CDC introduces into
the chemistry a paradigm shift with respect to constitutionally static chemistry and
opens new perspectives. It leads to the generation of chemical diversity within
constitutional dynamic libraries of compounds of either molecular (DCL, dynamic
covalent) or supramolecular (DNCL, dynamic non-covalent) nature. It enables adaptation through constitutional variation at both levels and thus opens towards an
adaptive chemistry whose entities are able to respond to physical stimuli or chemical
effectors.
2 Dynamers: Constitutional Dynamic Polymers
Application of the considerations above to polymer chemistry leads to the definition
of constitutionally dynamic polymers, dynamers, of both molecular and supramolecular types (Fig. 1) [29–32]. They behave as dynamic combinatorial entities,
based on dynamic libraries whose constituents have a combinatorial diversity
determined by the number of different monomers. The components incorporated
by polyassociation or by polycondensation into the supramolecular or molecular
polymer chains depend on the nature of the connections (recognition patterns or
functional groups) and core groups, as well as on the interactions with the environment, so that dynamers possess the capacity of adaptation by association/growth/
dissociation sequences.
Extending these notions to materials science in general, one may define constitutional dynamic materials as materials whose components are linked through
reversible covalent or non-covalent connections and undergo spontaneous and
continuous change in constitution by assembly/disassembly processes in a given
Dynamers: From Supramolecular Polymers to Adaptive Dynamic Polymers
157
linked through non-covalent interactions. But, now peace reigns and coexistence is
thriving for the mutual fertilization of the molecular and supramolecular chemistry
of polymeric entities, with active cross-talk between the two areas [22–32].
The topics covered in the present text will be limited to some aspects of the more
recent developments that have emerged from supramolecular chemistry and have been
carried over to polymer chemistry. They concern the implementation of a basic feature
of supramolecular chemistry, its dynamic character. Indeed, novel perspectives are
opened if one considers that supramolecular chemistry is intrinsically a dynamic
chemistry in view of the lability of the interactions connecting the molecular components of a supramolecular entity and its resulting ability to incorporate, decorporate,
and exchange its molecular components. It is thus a dynamic non-covalent chemistry
(DNCC). This dynamic character may be imported into molecular chemistry by
introducing into molecular entities covalent bonds that may form and break reversibly,
so as to allow for a continuous change in the covalent constitution by reorganization
and exchange of building blocks, . The resulting dynamic covalent chemistry (DCC)
has developed extensively in recent years [33–41]. DNCC and DCC have been brought
together under the unifying concept of constitutional dynamic chemistry (CDC)
[41–43] covering both the molecular and supramolecular areas. CDC introduces into
the chemistry a paradigm shift with respect to constitutionally static chemistry and
opens new perspectives. It leads to the generation of chemical diversity within
constitutional dynamic libraries of compounds of either molecular (DCL, dynamic
covalent) or supramolecular (DNCL, dynamic non-covalent) nature. It enables adaptation through constitutional variation at both levels and thus opens towards an
adaptive chemistry whose entities are able to respond to physical stimuli or chemical
effectors.
2 Dynamers: Constitutional Dynamic Polymers
Application of the considerations above to polymer chemistry leads to the definition
of constitutionally dynamic polymers, dynamers, of both molecular and supramolecular types (Fig. 1) [29–32]. They behave as dynamic combinatorial entities,
based on dynamic libraries whose constituents have a combinatorial diversity
determined by the number of different monomers. The components incorporated
by polyassociation or by polycondensation into the supramolecular or molecular
polymer chains depend on the nature of the connections (recognition patterns or
functional groups) and core groups, as well as on the interactions with the environment, so that dynamers possess the capacity of adaptation by association/growth/
dissociation sequences.
Extending these notions to materials science in general, one may define constitutional dynamic materials as materials whose components are linked through
reversible covalent or non-covalent connections and undergo spontaneous and
continuous change in constitution by assembly/disassembly processes in a given
Dynamers: From Supramolecular Polymers to Adaptive Dynamic Polymers
157