Complex Systems from Simple Building Blocks via Subcomponent Self-Assembly

Abstract

Subcomponent self-assembly allows for the construction of complexarchitectures from simple building blocks via the simultaneous,reversible formation of covalent and coordinative bonds. Complexstructures may be rapidly built by taking advantage of the differentand complementary selectivities of covalent and coordinative bond-formingreactions. Because both kinds of bonds are formed under thermodynamiccontrol, a wide variety of rearrangement reactions are possibleinvolving substitution at both intraligand and metal-ligandbonds. Understanding the selectivities that underlie these reactionsalso allows one to pick out specific products from among diversedynamic combinatorial libraries of interconverting structures. 1 Introduction 2 Initial Work 2.1 Aqueous Copper(I)-Templated Subcomponent Self-[nl]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 Imino-boronateEster Systems 9 Conclusions