Multifunctional hybrid materials composed of [60]fullerene-based functionalized-single-walled carbon nanotubes

Abstract We report the synthesis and characterization of several hybrid [60]fullerene–SWCNT materials that combine [60]fullerenes with appended photoactive ferrocenyl or porphyrinyl functionalities and SWCNTs into a single multifunctional structure, where the dyads are covalently attached to the exo-surface of SWCNTs. The structural properties of all hybrids have been characterized using a large variety of spectroscopic and HR-TEM techniques. Raman spectra showed how all SWCNTs were functionalized and the presence of functional groups in the nanotube derivatives. Furthermore, these spectra reveal a new electronic activity of the compounds due to the interaction of the functional groups with the SWCNT frameworks. XPS investigations have documented the presence of [60]fullerene derivatives around the exo-surface of the oxidized SWCNT walls, exhibiting a characteristic photoelectron N 1s emission peak at 400.3 eV. Very importantly, by means of HR-TEM investigations we have also observed the presence of the [60]fullerene functions on the SWCNT outer surface by imaging spherical structures. The presence of the porphyrinyl and ferrocenyl fragments, which can act as effective chromophores and electroactive species, makes this class of materials very interesting for applications in optoelectronics and photovoltaics, and bio-applications, for example in the field of diagnosis and treatment.

[1]  P. Masson,et al.  Fullerene-containing macromolecules for materials science applications , 2004 .

[2]  James Alastair McLaughlin,et al.  High resolution XPS characterization of chemical functionalised MWCNTs and SWCNTs , 2005 .

[3]  Nazario Martin,et al.  Materials for organic solar cells: the C60/pi-conjugated oligomer approach. , 2005, Chemical Society reviews.

[4]  S. Iijima.  Helical microtubules of graphitic carbon , 1991, Nature.

[5]  R. C. Johnson,et al.  HREELS and XPS Studies of Ferrocene on Ag(100) , 2000 .

[6]  A. Aurora,et al.  Metalloporphyrins as molecular precursors of electroactive hybrids: A characterization of their actual electronic states on Si(100) and (111) by AFM and XPS , 2007 .

[7]  Yi Lin,et al.  Functionalized carbon nanotubes: properties and applications. , 2002, Accounts of chemical research.

[8]  M. Prato,et al.  Novel Photoactive Single‐Walled Carbon Nanotube–Porphyrin Polymer Wraps: Efficient and Long‐Lived Intracomplex Charge Separation , 2005 .

[9]  Dirk M. Guldi,et al.  Fullerenes: From Synthesis to Optoelectronic Properties , 2002 .

[10]  S. C. O'brien,et al.  C60: Buckminsterfullerene , 1985, Nature.

[11]  M. Prato,et al.  [60]Fullerene as a substituent. , 2002, Chemistry.

[12]  Eduard Llobet,et al.  Oxygen functionalisation of MWNT and their use as gas sensitive thick-film layers , 2006 .

[13]  Maurizio Prato,et al.  Dendrimer-functionalized single-wall carbon nanotubes: synthesis, characterization, and photoinduced electron transfer. , 2006, Journal of the American Chemical Society.

[14]  M. Prato,et al.  Separation of metallic and semiconducting single-walled carbon nanotubes via covalent functionalization. , 2007, Small.

[15]  S. Campidelli,et al.  Liquid-crystalline fullerene-oligophenylenevinylene conjugates. , 2002, Chemical communications.

[16]  M. Prato,et al.  Integrating single-wall carbon nanotubes into donor-acceptor nanohybrids. , 2004, Angewandte Chemie.

[17]  Mercedes Alvaro,et al.  Synthesis, photochemistry, and electrochemistry of single-wall carbon nanotubes with pendent pyridyl groups and of their metal complexes with zinc porphyrin. Comparison with pyridyl-bearing fullerenes. , 2006, Journal of the American Chemical Society.

[18]  E. Menna,et al.  Selectivity of chemical oxidation attack of single-wall carbon nanotubes in solution , 2003 .

[19]  M. Seah,et al.  Practical Surface Analysis , 1992 .

[20]  Maurizio Prato,et al.  Double functionalization of carbon nanotubes for multimodal drug delivery. , 2006, Chemical communications.

[21]  E. Snow,et al.  Chemical vapor detection using single-walled carbon nanotubes. , 2006, Chemical Society reviews.

[22]  M. Prato,et al.  X-ray photoemission spectroscopy study on the effects of functionalization in fulleropyrrolidine and pyrrolidine derivatives , 2006 .

[23]  M. Dresselhaus,et al.  Optical transition energies for carbon nanotubes from resonant Raman spectroscopy: environment and temperature effects. , 2004, Physical review letters.

[24]  Shihe Yang,et al.  Synthesis and characterization of a grapevine nanostructure consisting of single-walled carbon nanotubes with covalently attached [60]fullerene balls. , 2008, Chemistry.

[25]  M. Prato,et al.  Chemistry of carbon nanotubes. , 2006, Chemical reviews.

[26]  Dirk M Guldi,et al.  Fullerene-porphyrin architectures; photosynthetic antenna and reaction center models. , 2002, Chemical Society reviews.

[27]  M. Prato,et al.  Functionalized carbon nanotubes in drug design and discovery. , 2008, Accounts of chemical research.

[28]  M. Prato,et al.  Functionalization and applications of []fullerene , 2006 .

[29]  Wei Xia,et al.  Surface characterization of oxygen-functionalized multi-walled carbon nanotubes by high-resolution X-ray photoelectron spectroscopy and temperature-programmed desorption , 2007 .

[30]  J. L. Delgado,et al.  The first synthesis of a conjugated hybrid of C60–fullerene and a single-wall carbon nanotube , 2007 .

[31]  F. Hauquier,et al.  Single-component and mixed ferrocene-terminated alkyl monolayers covalently bound to Si(111) surfaces. , 2006, The journal of physical chemistry. B.

[32]  F. Diederich,et al.  Photophysical and electrochemical properties of meso, meso-linked oligoporphyrin rods with appended fullerene terminals. , 2005, Chemphyschem : a European journal of chemical physics and physical chemistry.

[33]  A. N. Aleshin,et al.  Polymer Nanofibers and Nanotubes: Charge Transport and Device Applications , 2006 .

[34]  David Tománek,et al.  A novel hybrid carbon material. , 2007, Nature nanotechnology.

[35]  N. Armaroli.  Photoinduced Energy Transfer Processes in Functionalized Fullerenes , 2002 .

[36]  M. Prato,et al.  Synthesis, characterization, and photoinduced electron transfer in functionalized single wall carbon nanohorns. , 2007, Journal of the American Chemical Society.

[37]  M. Prato,et al.  Redox-active Si(100) surfaces covalently functionalised with [60]fullerene conjugates: new hybrid materials for molecular-based devices , 2008 .

[38]  Kirk J. Ziegler,et al.  Controlled oxidative cutting of single-walled carbon nanotubes. , 2005, Journal of the American Chemical Society.

[39]  Maurizio Prato,et al.  Fullerenes: multitask components in molecular machinery. , 2007, Angewandte Chemie.

[40]  Maurizio Prato,et al.  Functionalization of carbon nanotubes via 1,3-dipolar cycloadditions , 2004 .

[41]  Maurizio Prato,et al.  Nonlinear optical properties of ferrocene- and porphyrin-[60]fullerene dyads. , 2007, Chemphyschem : a European journal of chemical physics and physical chemistry.

[42]  Davide Bonifazi,et al.  Supramolecular [60]fullerene chemistry on surfaces. , 2007, Chemical Society reviews.

[43]  S. Campidelli,et al.  Functional polypedes?chiral nematic fullerenesElectronic supplementary information (ESI) available: purification procedures and analytical data for compounds 8 and 2. See http://www.rsc.org/suppdata/cc/b3/b303798n/ , 2003 .

[44]  P. Ajayan,et al.  Applications of Carbon Nanotubes , 2001 .

[45]  M. Prato,et al.  Spectroscopic changes induced by sonication of porphyrin–carbon nanotube composites in chlorinated solvents , 2007 .

[46]  R. Haddon.  Electronic structure, conductivity and superconductivity of alkali metal doped C60 , 1993 .

[47]  J. Clifford,et al.  Structure-dependent photoinduced electron transfer in fullerodendrimers with light-harvesting oligophenylenevinylene terminals. , 2006, Chemistry, an Asian journal.

[48]  N. Armaroli.  From metal complexes to fullerene arrays: exploring the exciting world of supramolecular photochemistry fifteen years after its birth , 2003, Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology.

[49]  V. Palermo,et al.  Pyrazolino[60]fullerene-oligophenylenevinylene dumbbell-shaped arrays: synthesis, electrochemistry, photophysics, and self-assembly on surfaces. , 2005, Chemistry.

[50]  Charles M Lieber,et al.  Fundamental electronic properties and applications of single-walled carbon nanotubes. , 2002, Accounts of chemical research.

[51]  A. Burden.  Materials for field emission displays , 2001 .

[52]  Zhijun Zhang,et al.  Formation of a Porphyrin Monolayer Film by Axial Ligation of Protoporphyrin IX Zinc to an Amino-Terminated Silanized Glass Surface , 2000 .

[53]  D. Briggs,et al.  High Resolution XPS of Organic Polymers: The Scienta ESCA300 Database , 1992 .

[54]  A. Hirsch.  Functionalization of single-walled carbon nanotubes. , 2002, Angewandte Chemie.

[55]  Dirk M Guldi,et al.  Multifunctional molecular carbon materials--from fullerenes to carbon nanotubes. , 2006, Chemical Society reviews.

[56]  F. Diederich,et al.  Oligoporphyrin arrays conjugated to [60] fullerene: Preparation, NMR analysis, and photophysical and electrochemical properties , 2005 .

[57]  M. Prato,et al.  Microscopic and spectroscopic characterization of paintbrush-like single-walled carbon nanotubes. , 2006, Nano letters.

[58]  Supramolecular hybrids of [60]fullerene and single-wall carbon nanotubes. , 2006, Chemistry.

[59]  M. Prato,et al.  Optical Limiting Applications , 2002 .

[60]  M. Prato,et al.  Control over electron transfer in tetrathiafulvalene-modified single-walled carbon nanotubes. , 2006, Angewandte Chemie.