Self-sorting

In the formation of complexes via self-sorting, no external template is used. Instead, the molecular structure of the host can be considered as the template for the preparation of a host-guest complex. In this case, the ampHfication of the most stable complex takes place via intermolecular interactions, such as hydrogen bonding, metal coordination, or ionic interactions, between the different components in the mixture. Since the strength of these supramolecular interactions is known to be influenced by substituents, a dynamic library can be obtained-not 

Self-sorting under kinetic control has also been reported [75]. However, due to the dynamic nature of the noncovalent interactions used in polymer self-assembly, the products of self-sorting usually cannot be isolated when they form in solution. 

Molecular recognition was used in a very elegant way to direct block copolymer morphology by Shenhar et al. [80]. Upon addition of dendritic wedges with thymine units to a lamellar block copolymer with diaminopyridine units, a block copolymer morphology was obtained after evaporation of the solvent. 

Self-sorting in polymers is not only of interest for multifunctionalization of polymers. Pollino et al. have shown that both functionalization and cross-linking can be done noncovalently in one step/pot by using the orthogonal assembly of palladium pincers with pyridine groups and thymine groups with diaminopyridine groups [94]. 

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Entry into Self-Sorting Research at the University of Maryland... 

ENTRY INTO SELF-SORTING RESEARCH AT THE UNIVERSITY OF MARYLAND... 

Scheme 4.3 Self-sorting based on thermodynamically controlled transesterification dnring macrocyclization of predisposed bnilding blocks.

Scheme 4.4 Self-sorting of 9 and 10 in the presence of barinm picrate leads to...

Scheme 4.6 Self-sorting behavior of C-shaped molecular clips 13 and ( )-14.

HOW IS SELF-SORTING DIFFERENT FROM SELF-ASSEMBLY ... 

How is Self-Sorting Different from Self-Assembly ... 

With proper design and implementation, however, it is possible to construct a self-sorting system whose behavior is different from its components [33c]. For example, consider the simple system comprising two hosts (A and B) and two guests (M and N) that can form four possible host-guest complexes (AM, AN, BM, and BN). We fix the total concentrations of hosts A and B ([A J and [B J) at 1 mM and choose the four equilibrium constants such that host A (KT-fold) and host B (10-fold) both prefer guest M (Scheme 4.7). The various mole fraction definitions (Scheme 4.7c) are used to construct a plot (Scheme 4.7d) of the composition of the mixture as a function of total guest concentration ([M J = [Nj J). When [AjJ = [Bj J > = [Nj j], complexes AM and BN dominate because... 

This section describes the development of self-sorting systems that has occurred in our laboratory over the past 5 years [34],... 

Figure 4.3 Chemical structures of compounds used for social self-sorting in aqueous solution driven by ion-dipole, metal-ligand, tt-tt, and hydrophobic interactions.

The CB[n] Family of Macrocycles are Prime Components for the Construction of Self-Sorting Systems... 

Scheme 4.9 Kinetic and thennodynamic self-sorting based on guests with two binding epitopes.

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