A new pyridyl-substituted methanofullerene derivative. Photophysics, electrochemistry and self-assembly with zinc(II) meso-tetraphenylporphyrin (ZnTPP)

A new methanofullerene derivative with a pyridine residue at the methano bridge (PC60) has been synthesized. Its electrochemical and photophysical properties have been investigated in toluene solution along with those of the analogous fullerene mono-malonate adduct RC60, which does not contain the pyridyl moiety. PC60 and RC60 display almost identical steady state absorption and luminescence properties and transient absorption spectra, as shown by means of nano- and picosecond laser flash photolysis. Their markedly different spectroscopic features with respect to plain C60 are discussed, with the aid of semi-empirical calculations. PC60 binds zinc(II) meso-tetraphenylporphyrin (ZnTPP) through coordination of the pyridyl moiety to the zinc ion giving, to the best of our knowledge, the first non-covalent assembly of a porphyrin–fullerene diad. The association constant of the 1:1 complex between PC60 and ZnTPP has been determined at 300 K by 1H NMR (Ka=3600±150 L mol-1, C6D6 solution) and fluorescence titrations (Ka=3000±400 L mol-1, toluene solution). Mixtures of RC60 and ZnTPP have also been investigated, giving no evidence of association. Extremely fast ZnTPP luminescence quenching in the PC60–ZnTPP complex was observed by time-resolved luminescence spectroscopy (k>5×1010 s-1), tentatively attributed to an energy transfer mechanism. The bimolecular quenching constant of the lowest triplet excited state of ZnTPP by PC60 was determined via a Stern–Volmer analysis (kq=6.7×109 s-1).

[1]  F. Diederich,et al.  PTII-DIRECTED SELF-ASSEMBLY OF A DINUCLEAR CYCLOPHANE CONTAINING TWO FULLERENES , 1998 .

[2]  O. Ito,et al.  PHOTOINDUCED ELECTRON TRANSFER BETWEEN C60/C70 AND ZINC TETRAPHENYLPORPHYRIN IN POLAR SOLVENTS , 1998 .

[3]  Thomas A. Moore,et al.  Light-driven production of ATP catalysed by F0F1-ATP synthase in an artificial photosynthetic membrane , 1998, Nature.

[4]  Jason E. Riggs,et al.  Photophysical and Nonlinear Optical Properties of [60]Fullerene Derivatives† , 1998 .

[5]  A. Burrell,et al.  Controlling the Structure of Supramolecular Porphyrin Arrays , 1998 .

[6]  V. Balzani,et al.  Designing Dendrimers Based on Transition-Metal Complexes. Light-Harvesting Properties and Predetermined Redox Patterns , 1998 .

[7]  M. Ward.  Photo-induced electron and energy transfer in non-covalently bonded supramolecular assemblies , 1998 .

[8]  H. Imahori,et al.  A Sequential Photoinduced Electron Relay Accelerated by Fullerene in a Porphyrin‐Pyromellitimide‐C60 Triad , 1997 .

[9]  J. F. Stoddart,et al.  Self-Assembly of the First Fullerene-Containing [2]Catenane† , 1997 .

[10]  V. Balzani,et al.  Photoinduced Processes in Dyads Made of a Porphyrin Unit and a Ruthenium Complex , 1997 .

[11]  M. Paddon-Row,et al.  Long-lived photoinduced charge separation in a bridged C60-porphyrin dyad , 1997 .

[12]  A. Moore,et al.  Photoinduced Charge Separation and Charge Recombination to a Triplet State in a Carotene−Porphyrin−Fullerene Triad , 1997 .

[13]  F. Diederich,et al.  Methanofullerene Molecular Scaffolding: Towards C60-substituted poly(triacetylenes) and expanded radialenes, preparation of a C60–C70 hybrid derivative, and a novel macrocyclization reaction , 1997 .

[14]  T. Moore,et al.  Fullerenes linked to photosynthetic pigments , 1997 .

[15]  Seiji Taniguchi,et al.  Linkage and Solvent Dependence of Photoinduced Electron Transfer in Zincporphyrin-C60 Dyads , 1996 .

[16]  T. Moore,et al.  Energy and Photoinduced Electron Transfer in Porphyrin−Fullerene Dyads , 1996 .

[17]  Christopher A. Hunter,et al.  Photoinduced Energy and Electron Transfer in Supramolecular Porphyrin Assemblies , 1996 .

[18]  M. Prato,et al.  Synthesis, Chiroptical Properties, and Configurational Assignment of Fulleroproline Derivatives and Peptides , 1996 .

[19]  W. B. Caldwell,et al.  Thin film, fullerene-based materials , 1996 .

[20]  Vincenzo Balzani,et al.  Luminescent and Redox-Active Polynuclear Transition Metal Complexes. , 1996, Chemical reviews.

[21]  Yuan-Pern Lee,et al.  Laser-induced fluorescence and phosphoresence of C isolated in solid Ne , 1996 .

[22]  François Diederich,et al.  Covalent Fullerene Chemistry , 1996, Science.

[23]  A. Harriman,et al.  A strategy for constructing photosynthetic models: porphyrin-containing modules assembled around transition metals , 1996 .

[24]  M. Prato,et al.  Photoinduced electron transfer and long lived charge separation in a donor-bridge-acceptor supramolecular ‘diad’ consisting of ruthenium(II) tris(bipyridine) functionalized C60 , 1995 .

[25]  F. Diederich,et al.  Electrochemistry of Mono‐ through Hexakis‐adducts of C60 , 1995 .

[26]  P. A. Lay,et al.  Solvent effects on the electronic spectrum of C , 1995 .

[27]  Jan W. Verhoeven,et al.  Photoinduced intramolecular electron transfer in a bridged C60(Acceptor)-Aniline(Donor)system. Photophysical properties of the first active fullerene Diad , 1995 .

[28]  W. Kühlbrandt.  Many wheels make light work , 1995, Nature.

[29]  B. Wang,et al.  Photoinduced energy transfer in associated, but noncovalently-linked photosynthetic model systems. , 1995 .

[30]  Jan F. Schmidt,et al.  Phosphorescence of C60 at 1.2 K , 1994 .

[31]  C. Hunter,et al.  Self‐Assembly of a Dimeric Porphyrin Host , 1994 .

[32]  T. Moore,et al.  PREPARATION AND PHOTOPHYSICAL STUDIES OF PORPHYRIN‐C60 DYADS , 1994 .

[33]  Yves Rubin,et al.  Photophysical Characterization and Singlet Oxygen Yield of a Dihydrofullerene , 1994 .

[34]  C. Bignozzi,et al.  Vibrational and electronic spectroscopy of electronically excited polychromophoric ruthenium(II) complexes , 1994 .

[35]  J. Sworakowski,et al.  A photoluminescence study of fullerenes: total luminescence spectroscopy of C60 and C70 , 1993 .

[36]  L. Flamigni.  Inclusion of fluorescein and halogenated derivatives in .alpha.-, .beta.-, and .gamma.-cyclodextrins: a steady-state and picosecond time-resolved study , 1993 .

[37]  Carsten Bingel,et al.  Cyclopropanierung von Fullerenen , 1993 .

[38]  Thomas A. Moore,et al.  Molecular mimicry of photosynthetic energy and electron transfer , 1993 .

[39]  L. Flamigni.  A nanosecond laser-flash-photolysis study of intramicellar reactions in the erythrosin B/CTAB aqueous system , 1992 .

[40]  M. Wasielewski.  Photoinduced electron transfer in supramolecular systems for artificial photosynthesis , 1992 .

[41]  A. Harriman,et al.  Charge transfer across oblique bisporphyrins: two-center photoactive molecules , 1991 .

[42]  M. Grätzel,et al.  A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films , 1991, Nature.

[43]  Michael Grätzel,et al.  The Artificial Leaf, Molecular Photovoltaics Achieve Efficient Generation of Electricity from Sunlight , 1991 .

[44]  Robert L. Whetten,et al.  Photophysical properties of C60 , 1991 .

[45]  J. Scaiano,et al.  Effect of cyclodextrin complexation on the photochemistry of xanthone. Absolute measurement of the kinetics for triplet-state exit , 1990 .

[46]  A. Osuka,et al.  A chemical approach toward photosynthetic reaction center , 1990 .

[47]  J. Barber.  Electron-transfer theory in question , 1988, Nature.

[48]  Michael C. Zerner,et al.  Calculated spectra of hydrated ions of the first transition-metal series , 1986 .

[49]  Edward M. Kober,et al.  Application of the energy gap law to excited-state decay of osmium(II)-polypyridine complexes: calculation of relative nonradiative decay rates from emission spectral profiles , 1986 .

[50]  Michael G. Kinnaird,et al.  Artificial allosteric system. 2. Cooperative 1-methylimidazole binding to an artificial allosteric system, zinc-gable porphyrin-dipyridylmethane complex , 1985 .

[51]  Katsumi Nakamaru.  Synthesis, Luminescence Quantum Yields, and Lifetimes of Trischelated Ruthenium(II) Mixed-ligand Complexes Including 3,3′-Dimethyl-2,2′-bipyridyl , 1982 .

[52]  J. Demas,et al.  Measurement of photoluminescence quantum yields. Review , 1971 .

[53]  Joel H. Hildebrand,et al.  A Spectrophotometric Investigation of the Interaction of Iodine with Aromatic Hydrocarbons , 1949 .