Chemistry Reference
In-Depth Information
CHAPTER 1
A BRIEF INTRODUCTION TO
SUPRAMOLECULAR CHEMISTRY
IN A POLYMER CONTEXT
RAYMOND J. THIBAULT and VINCENT M. ROTELLO
1.1. INTRODUCTION AND BACKGROUND
Self-assembly of molecular and macromolecular systems is a versatile and modular
tool for the creation of higher order structures (Lehn 1993). Nature employs self-
assembly extensively using both phase segregation and “lock and key” specific inter-
actions to generate the diverse range of highly ordered systems observed in living
organisms. Applying biologically inspired self-assembly strategies to synthetic
macromolecules provides access to a wide range of desirable structural and
dynamic properties. Controlled noncovalent interactions are a particularly attractive
strategy for controlling polymer aggregation, using the array of recognition elements
developed by supramolecular chemists. The modularity and tunability of these recog-
nition elements makes this approach versatile, because the assembling units can be
synthetically tuned to enhance or minimize selectivity, directionality, and the affinity
of the interaction. Likewise, the affinity of noncovalent interactions is thermally
dependent, imparting reversibility to the assembly process and providing unique
material properties such as defect correction and self-healing capabilities.
The toolkit of interactions available for supramolecular polymers can be divided
into the six categories listed in Table 1.1 that includes hydrophobic interactions,
which are dealt with in more detail in Chapter 2.
In this chapter, we present a brief overview of supramolecular polymers and
polymerization and supramolecular interactions of polymer side chains. We provide
examples of the control over the solution state polymer structure that can be achieved
at the molecular level and then extended to micro- and macroscale assemblies.
