Synlett 2008(20): 3077-3090  
DOI: 10.1055/s-0028-1087361
ACCOUNT
© Georg Thieme Verlag Stuttgart ˙ New York

Complex Systems from Simple Building Blocks via Subcomponent Self-Assembly

Victoria E. Campbell, Jonathan R. Nitschke*
The University Chemical Laboratory, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK
Fax: +44(1223)336362; e-Mail: jrn34@cam.ac.uk;
Further Information

Publication History

Received 19 May 2008
Publication Date:
24 November 2008 (online)

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