Making new supermolecules for the next century: Multipurpose reagents fromethynyl-grafted oligopyridines

Synthetic routes towards the construction of molecular-scale wires and inor dinately stable free radicals bearing acetylenic units are presented. They comprise the sequential cross-coupling reactions between ethynylated syntho ns and the corresponding oligopyridine derivatives and provide access to va rious rationally designed multitopic ligands. The stepwise preparation of m ultifunctional molecules displaying a central metallic platform and the use of metallo-synthons in Sonogahira coupling reaction promoted by low valent palladium(0) is also presented. This method was extended to the synthesis of molecules bearing a persistent nitronyl nitroxide radical. 1 Introduction 2 Synthesis of Polytopic Ligands Bearing sp-Hydridized Carbon Chains as Spa cers 2.1 Building Blocks with a Single Acetylenic Bond 2.2 Building Blocks with a Two or Three Acetylenic Bonds 2.3 Construction of Multitopic Ligands 2.4 Application to Metal-Directed Self-organization Processes 2.5 Application to Photo-Induced Intramolecular Triplet Energy Transfer 2.6 Application to Polymers by Electro polymerisation 3 Divergent Synthesis of Pre-Formed Metallo-Synthons 3.1 Use of (n-Bu3P)(2)Pt Platforms 3.2 Tailor-made Complexes and Synthetic Tools 3.3 Application to Intramolecular Triplet Energy Transfer 3.4 Application to Detection of Adventitious Cations 4 Ethynyl-Functionalized Stable Organic Radicals 4.1 Monoradical Family 4.2 Elongated Ethynylene-Bridged Radicals 4.3 Magnetic Properties of Selected Compounds 5 Conclusions, Outlook and Perpectives.