Abstract
Subcomponent self-assembly allows for the construction of complex
architectures from simple building blocks via the simultaneous,
reversible formation of covalent and coordinative bonds. Complex
structures may be rapidly built by taking advantage of the different
and complementary selectivities of covalent and coordinative bond-forming
reactions. Because both kinds of bonds are formed under thermodynamic
control, a wide variety of rearrangement reactions are possible
involving substitution at both intraligand and metal-ligand
bonds. Understanding the selectivities that underlie these reactions
also allows one to pick out specific products from among diverse
dynamic combinatorial libraries of interconverting structures.
1 Introduction
2 Initial Work
2.1 Aqueous Copper(I)-Templated Subcomponent Self- Assembly
3 Construction
3.1 Dicopper and Tricopper Helicates
3.2 Tetracopper(I) Grid
3.3 Catenates and Macrocycles
4 Rearrangements
4.1 Cascade Reaction
4.2 Electronic Effects
5 Sorting
5.1 Sorting Ligand Structures with Copper(I)
5.2 Cooperative Selection by Iron and Copper
5.3 Sorting within a Structure
6 Systems Chemistry
6.1 Deterministic Self-Sorting Systems of Subcomponents
6.2 Interplay between Three Dynamic Equilibria
7 Chiral Information Transfer
7.1 Chirality Transfer from Carbon to Copper(I)
7.2 Chiral Resolution during Crystallization
8 Boron-Templated Self-Assembly
8.1 Mononuclear Boron-Templated Structures
8.2 More-Complex Structures
8.3 Subcomponent Substitution Reactions within Iminoboronate
Ester Systems
9 Conclusions
Key words
subcomponent self-assembly - dynamic combinatorial chemistry - systems chemistry - coordination chemistry - dynamic
covalent chemistry