Shane O. Mc Donnell, Giuseppe Sforazzini , Johannes K. Sprafke and Harry L. Anderson

1. Conjugated Polymers Threaded Through Macrocycles 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 • Organic-Soluble Polyrotaxanes • Giuseppe Sforazzini Molecular Mechanics Polyrotaxanes with charge-transporting substituents Synthesis of Non-polar Polyrotaxane Threaded Molecuar Wires Calculated structures of polymers. (a) PFBP.Bn, (b) PFBP.Hβ‑CD (c) PFBP.BnβCD.Bn, (d) PFBP.Meβ‑CD.Si Minimizations conducted using the MMFFs force field. Solvent: CHCl3 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. Modification of water-soluble polyrotaxanes1 (PFBP.Liβ‑CD) has given polyrotaxanes that are soluble in organic solvents such as CHCl3, CH2Cl2, THF and benzene, and free from ionic impurities.2 conjugated polymer core— hole transport cyclodextrin insulation sheath— electron transport 1Frampton, M. J., Anderson, H. L., Angew. Chem. Int. Ed.2007, 46, 1028; 2M. 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 Sulfur Functionalised Rotaxanes Shane Mc Donnell Synthesis Nanoparticle Assembly Molecular Ordering The versatile polyrotaxane structure allows for simple modification of components. Functionalisation of stopper components with sulfur rich appendages facilitates contact to metal surfaces. Aurochloric acid is reduced by sodium borohydride and the Au0 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. 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. Controlled gold nanoparticle growth leads to tuning of the opto-electronic properties. Chem. Soc. Rev. 2006, 35, 209 Synthesis of both naked and encapsulated stilbene units, each containing sulfur appendages. PorphyrinNanorings and Tubes Johannes Sprafke Bending of Linear Porphyrin Wires 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 Octamer1 and a cyclic hexamer2. 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. Target Structure References: 1M. Hoffmann, H. L. Anderson et al., Angew. Chem. Intl. Ed. 2007, 46, 3122. 2M. Hoffmann, H. L. Anderson et al., submitted. Funding: Regione Sardegna Scholarship, EPSRC and the European Comission (Project THREADMILL – MRTN-CT-2006-036040)