1. Shane O. Mc Donnell, Giuseppe Sforazzini, Johannes K. Sprafke and Harry L. Anderson Department of Chemistry, University of Oxford, 12 Mansfield Road, Oxford, OX1 3TA, UK harry.anderson@chem.ox.ac.uk Conjugated Polymers Threaded Through Macrocycles Funding: Regione Sardegna Scholarship, EPSRC and the European Comission (Project THREADMILL – MRTN-CT-2006-036040) Porphyrin Nanorings and Tubes Johannes Sprafke A Porphyrin Nanoring With A “Sticky” Rim Formation of Tubular Structures Recently our group demonstrated the flexibility of conjugated butadiyne linked porphyrin oligomers with the synthesis of a cyclic Octamer 1 and a cyclic hexamer 2. A template was used to bend linear oligomers, followed by Palladium catalysed ring closure. Current work is directed towards the synthesis of a derivative of the cyclic hexamer with carboxylic acids on one rim of the ring. These carboxyl groups can be used to bind guests, attach the molecule to surfaces or to form dimers by hydrogen bonding. A new ring featuring carboxyl groups on both rims is designed to form long tubular structures. Theses tubes will then be used for encapsulation of conjugated polymers or carbon nanotubes. References: 1 M. Hoffmann, H. L. Anderson et al., Angew. Chem. Intl. Ed. 2007, 46, 3122. 2 M. Hoffmann, H. L. Anderson et al., submitted. Bending of Linear Porphyrin Wires Target Structure Modification of water-soluble polyrotaxanes 1 (PFBP.Li  β ‑ CD) has given polyrotaxanes that are soluble in organic solvents such as CHCl 3, CH 2 Cl 2, THF and benzene, and free from ionic impurities. 2 Organic-Soluble Polyrotaxanes Giuseppe Sforazzini 1 Frampton, M. J., Anderson, H. L., Angew. Chem. Int. Ed. 2007, 46, 1028; 2 M. J. Frampton, G. Sforazzini, E. Townsend., C. C. Williams, A. Charas, N. S. Kaka, M. Sirish, G. Latini, L. J. Parrott, S. Brovelli, J. S. Wilson, F. Cacialli and H. L. Anderson. Adv. Funct. Mater., manuscript in preparation conjugated polymer core — hole transport cyclodextrin insulation sheath — electron transport Molecular Mechanics Synthesis of Non-polar Polyrotaxane Threaded Molecuar Wires Calculated structures of polymers. (a) PFBP.Bn, (b) PFBP.H  β ‑ CD (c) PFBP.Bn  β CD.Bn, (d) PFBP.Me  β ‑ CD.Si Minimizations conducted using the MMFFs force field. Solvent: CHCl 3 for (a), (c) and (d); water for (b). Current work is directed toward the synthesis of polyrotaxane insulated molecular wire with a charge-transport shell (a). Incorporation of electron acceptors such as fullerenes (b) should lead to promising photovoltaic materials. Polyrotaxanes with charge-transporting substituents Sulfur Functionalised Rotaxanes Shane Mc Donnell The versatile polyrotaxane structure allows for simple modification of components. Functionalisation of stopper components with sulfur rich appendages facilitates contact to metal surfaces. Controlled gold nanoparticle growth leads to tuning of the opto-electronic properties. Chem. Soc. Rev. 2006, 35, 209 Aurochloric acid is reduced by sodium borohydride and the Au 0 species is capped with an SAM of alkane thiols. J. Chem. Soc. Chem. Commun. 1994, 801 Energy minimised cystamine-[2]rotaxane structure. TEM of gold nanoparticles. Top dodecane thiol stablised particles. Bottom post ligand exchange with 1 revealed particle diameters that were not significantly modified by reaction conditions. Measured by Dr. H. Wang, Oxford University. Synthesis of both naked and encapsulated stilbene units, each containing sulfur appendages. Left: α-Cyclodexrin. Middle: Chemisorbed 2 on flat Au (111) surface. Right: Using STM and AFM the molecular order and electrical conductivity properties of both 1 and 2 on Au (111) surface are now under way at Samori Group, ULP, Strasbourg. Molecular Ordering Synthesis Nanoparticle Assembly