Synthesis of fullerene adducts with terpyridyl- or pyridylpyrrolidine groups in trans-1 positions.

Two C(60) hexakis-adducts (2 and 3) were synthesized by using a protection-deprotection strategy. The symmetric fullerene tetrakis-adduct 8 was obtained by anthracene removal from the hexakis-adduct 7. Reaction of 8 with terpyridylglycine or pyridylglycine afforded two hexakis-adducts, 2 and 3. By using the retro-cyclopropanation reaction, the four malonate addends located on the equatorial belt of the hexakis-adducts were removed to afford two trans-1 bis-adducts, 4 and 5, with terpyridyl- or pyridylpyrrolidine groups. The structures of 2 and 3 were confirmed by matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, and (1)H, (13)C, and COSY NMR, and UV-visible spectroscopy. The cyclic voltammograms of fullerene multiadducts 2, 3, and 9 show irreversible reductions. Self-assembled monolayers (SAMs) of 1 and 3 were formed on gold surfaces through nitrogen adsorption. SAMs of 3 represent the first example of a fullerene hexakis-adduct formed on gold surfaces through nitrogen adsorption. Controlled potential electrolyses (CPE) were conducted to prepare trans-1 bis-adducts 4 and 5 modified with terpyridyl and pyridyl groups.

[1]  M. Ohta,et al.  Synthesen von N -(4-Pyridyl)glycine , 1960 .

[2]  Y. Obeng,et al.  Electrochemistry and Langmuir Trough Studies of C60 and C70 Films , 1992 .

[3]  R. Moriarty,et al.  Crown ether ionophores. Construction of neutral carrier ion-selective electrodes , 1993 .

[4]  Heinrich R. Karfunkel,et al.  Fullerenchemie in drei Dimensionen: Isolierung von sieben regioisomeren Bisaddukten sowie chiralen Trisaddukten aus C60 und Di(ethoxycarbonyl)methylen , 1994 .

[5]  W. B. Caldwell,et al.  A WELL-DEFINED SURFACE-CONFINABLE FULLERENE : MONOLAYER SELF-ASSEMBLY ON AU(111) , 1994 .

[6]  François Diederich,et al.  Spacer‐kontrollierte Fernfunktionalisierung von Buckminsterfulleren: regiospezifische Bildung eines Hexaadduktes , 1994 .

[7]  F. Diederich,et al.  Tether-Directed Remote Functionalization of Buckminsterfullerene: Regiospecific Hexaadduct Formation† , 1994 .

[8]  A. Hirsch,et al.  Fullerene Chemistry in Three Dimensions: Isolation of Seven Regioisomeric Bisadducts and Chiral Trisadducts of C60 and Di(ethoxycarbonyl)methylene , 1994 .

[9]  J. Hummelen,et al.  Polymer Photovoltaic Cells: Enhanced Efficiencies via a Network of Internal Donor-Acceptor Heterojunctions , 1995, Science.

[10]  T. Müller,et al.  A Topochemically Controlled, Regiospecific Fullerene Bisfunctionalization , 1996 .

[11]  D. Schwarzenbach,et al.  Eine topochemisch kontrollierte, regiospezifische Fulleren‐Bisfunktionalisierung , 1996 .

[12]  A. Hirsch,et al.  Regiochemistry of Twofold Additions to [6,6] Bonds in C60: Influence of the Addend‐Independent Cage Distortion in 1,2‐Monoadducts , 1996 .

[13]  Stephen R. Wilson,et al.  Interfacial Hydrogen Bonding. Self-Assembly of a Monolayer of a Fullerene−Crown Ether Derivative on Gold Surfaces Derivatized with an Ammonium-Terminated Alkanethiolate , 1996 .

[14]  Neil G. Connelly,et al.  Chemical Redox Agents for Organometallic Chemistry. , 1996, Chemical reviews.

[15]  M. Ward,et al.  Ruthenium(II) complexes of some new polynucleating ligands incorporating terpyridyl and macrocyclic aza-crown binding sites , 1996 .

[16]  Stephen R. Wilson,et al.  Preparation and Characterization of Six Bis(N-methylpyrrolidine)−C60 Isomers: Magnetic Deshielding in Isomeric Bisadducts of C60 , 1996 .

[17]  M. Prato,et al.  USE OF TRANSIENT EPR SPECTROSCOPY OF EXCITED TRIPLET STATE FOR THE STRUCTURAL ASSIGNMENT OF BISADDUCTS OF FULLERENE C60 , 1997 .

[18]  M. Reed,et al.  Conductance of a Molecular Junction , 1997 .

[19]  Maurizio Prato,et al.  [60]Fullerene chemistry for materials science applications , 1997 .

[20]  T. Müller,et al.  Concise Route to Symmetric Multiadducts of [60]Fullerene: Preparation of an Equatorial Tetraadduct by Orthogonal Transposition , 1997 .

[21]  Christian Joachim,et al.  CONDUCTANCE AND TRANSPARENCE OF LONG MOLECULAR WIRES , 1997 .

[22]  F. Diederich,et al.  Regioselektive, durch einen Kronenether- Spacer kontrollierte Synthese vontrans-1- Fulleren-Bisaddukten: Alkalimetallionen- abhängige Redoxeigenschaften von Fulleren-Kronenether-Konjugaten , 1998 .

[23]  F. Diederich,et al.  Regioselective Synthesis of trans-1 Fullerene Bis-Adducts Directed by a Crown Ether Tether: Alkali Metal Cation Modulated Redox Properties of Fullerene-Crown Ether Conjugates. , 1998, Angewandte Chemie.

[24]  M. Prato,et al.  Fulleropyrrolidines: A Family of Full-Fledged Fullerene Derivatives , 1998 .

[25]  S. Tans,et al.  Room-temperature transistor based on a single carbon nanotube , 1998, Nature.

[26]  A. Herrmann,et al.  HERSTELLUNG VON ENANTIOMERENREINEM C76 DURCH RETRO-BINGEL-REAKTION , 1998 .

[27]  Yuyuan Tian,et al.  Self-assembled fullerene-derivative monolayers on a gold substrate using phenanthroline-Au interactions , 1998 .

[28]  F. Diederich,et al.  Preparation of Enantiomerically Pure C76 with a General Electrochemical Method for the Removal of Di(alkoxycarbonyl)methano Bridges from Methanofullerenes: The Retro-Bingel Reaction , 1998 .

[29]  Wenyuan Qian,et al.  Auf dem Weg zur vollständigen Kontrolle der sechsfachen Funktionalisierung von Buckminsterfulleren (C60) an oktaedrischen Positionen , 1999 .

[30]  F. Diederich,et al.  Cyclophane-type fullerene-dibenzo[18]crown-6 conjugates with trans-1, trans-2, and trans-3 addition patterns: Regioselective templated synthesis, x-ray crystal structure, ionophoric properties, and cation-complexation- dependent redox behavior , 1999 .

[31]  François Diederich,et al.  Supramolecular fullerene chemistry , 1999 .

[32]  A. Herrmann,et al.  Die Chemie von C84: Trennung von drei Konstitutionsisomeren des Fullerens C84 und der Enantiomere von D2-C84 durch die „Bingel-Retro-Bingel”-Strategie , 1999 .

[33]  H. Imahori,et al.  Photoinduced electron transfer at a gold electrode modified with a self-assembled monolayer of fullerene , 1999 .

[34]  Qian,et al.  Towards Sixfold Functionalization of Buckminsterfullerene (C(60)) at Fully Addressable Octahedral Sites. , 1999, Angewandte Chemie.

[35]  F. Diederich,et al.  Chemistry of C84 : Separation of Three Constitutional Isomers and Optical Resolution of D2 -C84 by Using the "Bingel-Retro-Bingel" Strategy. , 1999, Angewandte Chemie.

[36]  Paul L. McEuen,et al.  Nanomechanical oscillations in a single-C60 transistor , 2000, Nature.

[37]  M. Prato,et al.  Stepwise Assembled Photoactive Films Containing Donor-Linked Fullerenes. , 2000, Angewandte Chemie.

[38]  Yves Rubin,et al.  A Parallel Library of all Seven A2+B2+C2Th Regioisomeric Hexakisadducts of Fullerene C60: Inspiration from Werner's Octahedral Stereoisomerism , 2000 .

[39]  F. Diederich,et al.  Redox-active self-assembled monolayers as novel solid contacts for ion-selective electrodes , 2000 .

[40]  Maurizio Prato,et al.  Schichtweise Organisation photoaktiver Filme auf der Basis von Donor-verknüpften Fullerenen , 2000 .

[41]  Nicola Armaroli,et al.  Charge-transfer interactions in face-to-face porphyrin-fullerene systems: solvent-dependent luminescence in the infrared spectral region , 2000, Chemistry.

[42]  John K. Tomfohr,et al.  Reproducible Measurement of Single-Molecule Conductivity , 2001, Science.

[43]  Chunhui Huang,et al.  Photoelectric response of a gold electrode modified with self-assembled monolayers of pyrrolidinofullerenes , 2001 .

[44]  Daoben Zhu,et al.  The self-assembly of [60]fullerene-substituted 2,2′-bipyridine on the surface of Au(111) and Au nanoparticles , 2001 .

[45]  D. Labaree,et al.  Synthesis of halogen-substituted pyridyl and pyrimidyl derivatives of [3,2-c]pyrazolo corticosteroids: strategies for the development of glucocorticoid receptor mediated imaging agents. , 2002, Journal of medicinal chemistry.

[46]  Jonas I. Goldsmith,et al.  Coulomb blockade and the Kondo effect in single-atom transistors , 2002, Nature.

[47]  L. Echegoyen,et al.  Self-assembled monolayers of different conformers of p-tert-butylcalix[4]crown-6 derivatives and their metal cation recognition properties , 2003 .

[48]  The Kondo effect in C60 single-molecule transistors , 2003, cond-mat/0310625.

[49]  R. Nichols,et al.  Redox state dependence of single molecule conductivity. , 2003, Journal of the American Chemical Society.

[50]  M. Fischer,et al.  Elektrischer Strom durch ein Molekül – Einfluss der Position der Ankergruppen , 2003 .

[51]  K. L. Sebastian,et al.  Dynamics of vibrational excitation in the C 60 single-molecule transistor , 2003 .

[52]  Marcel Mayor,et al.  Electric current through a molecular rod-relevance of the position of the anchor groups. , 2003, Angewandte Chemie.

[53]  J. C. Tsang,et al.  Electrically Induced Optical Emission from a Carbon Nanotube FET , 2003, Science.

[54]  Jean-Luc Brédas,et al.  Single-electron transistor of a single organic molecule with access to several redox states , 2003, Nature.

[55]  Stephen R. Wilson,et al.  Synthesis and photophysics of a linear non-covalently linked porphyrin-fullerene dyad. , 2003, Chemical communications.

[56]  L. Echegoyen,et al.  Synthesis, Self‐Assembled Monolayers and Alkaline Earth Metal Ion Recognition of p‐tert‐Butylcalix[4]arene Derivatives , 2004 .

[57]  D. Ralph,et al.  The Kondo Effect in the Presence of Ferromagnetism , 2004, Science.

[58]  F. Diederich,et al.  Electrochemically Induced Retro‐Cyclopropanation Reactions , 2004 .

[59]  Stephen R. Wilson,et al.  A new fullerene complexation ligand: N-pyridylfulleropyrrolidine. , 2004, The Journal of organic chemistry.

[60]  L. Echegoyen,et al.  Selective binding of aromatic amines by self-assembled monolayers of a calix[6]crown-4 derivative. , 2004, Organic letters.

[61]  T. Bjørnholm,et al.  Self-Assembly and Conductive Properties of Molecularly Linked Gold Nanowires , 2004 .

[62]  C. Housecroft,et al.  A Convenient Synthesis of Multitopic 2,2′:6′,2′′-Terpyridine Ligands , 2004 .

[63]  A. Merbach,et al.  Novel heteroditopic chelate for self-assembled gadolinium(III) complex with high relaxivity. , 2004, Chemical communications.

[64]  C. Silien,et al.  Tuning the bipolar conductance of an alkali-doped C(60) layer sandwiched between two tunneling barriers. , 2005, Nano letters.

[65]  Yuyuan Tian,et al.  Electromechanical and conductance switching properties of single oligothiophene molecules. , 2005, Nano letters.

[66]  L. Echegoyen,et al.  Noncovalent Immobilization of C60 on Gold Surfaces by SAMs of Cyclotriveratrylene Derivatives , 2005 .

[67]  M. Prato,et al.  Isolation and characterization of nine tris-adducts of N-methylfulleropyrrolidine derivatives. , 2005, The Journal of organic chemistry.

[68]  Dongho Kim,et al.  Photovoltaic cells using composite nanoclusters of porphyrins and fullerenes with gold nanoparticles. , 2005, Journal of the American Chemical Society.

[69]  J. Kong,et al.  Orbital Kondo effect in carbon nanotubes , 2005, Nature.

[70]  Yuyuan Tian,et al.  Large gate modulation in the current of a room temperature single molecule transistor. , 2005, Journal of the American Chemical Society.

[71]  L. Echegoyen,et al.  Selective anion sensing by a tris-amide CTV derivative: 1H NMR titration, self-assembled monolayers, and impedance spectroscopy. , 2005, Journal of the American Chemical Society.