Selective Extraction of C70 by a Tetragonal Prismatic Porphyrin Cage.

Along with the advent of supramolecular chemistry, research on fullerene receptors based on noncovalent bonding interactions has attracted a lot of attention. Here, we present the design and synthesis of a cationic molecular cage: a cyclophane composed of two tetraphenylporphyrins, bridged face-to-face by four viologen units in a rhomboid prismatic manner. The large cavity inside the cage, as well as the favorable donor-acceptor interactions between the porphyrin panels and the fullerene guests, enables the cage to be an excellent fullerene receptor. The 1:1 host-guest complexes formed between the cage and both C60 and C70 were characterized in solution by HRMS and NMR, UV-vis and fluorescence spectroscopies, and confirmed in the solid state by single-crystal X-ray diffraction analyses. The results from solution studies reveal that the cage has a much stronger binding for C70 than for C60, resulting in a selective extraction of C70 from a C60-enriched fullerene mixture (C60/C70 = 10/1), demonstrating the potential of the cage as an attractive receptor for fullerene separation.

[1]  J. C. Barnes,et al.  ExCage , 2020, Catalysis from A to Z.

[2]  F. Gándara,et al.  Purification of Uranium-based Endohedral Metallofullerenes (EMFs) by Selective Supramolecular Encapsulation and Release. , 2018, Angewandte Chemie.

[3]  Shangfeng Yang,et al.  A Three-Dimensional Capsule-like Carbon Nanocage as a Segment Model of Capped Zigzag [12,0] Carbon Nanotubes: Synthesis, Characterization, and Complexation with C70. , 2018, Angewandte Chemie.

[4]  J. F. Stoddart,et al.  ExTzBox: A Glowing Cyclophane for Live-Cell Imaging. , 2018, Journal of the American Chemical Society.

[5]  Ryan M. Young,et al.  Toward a Charged Homo[2]catenane Employing Diazaperopyrenium Homophilic Recognition. , 2018, Journal of the American Chemical Society.

[6]  Florian Beuerle,et al.  Covalent Organic Frameworks and Cage Compounds: Design and Applications of Polymeric and Discrete Organic Scaffolds. , 2018, Angewandte Chemie.

[7]  Feihe Huang,et al.  Platinum(II)-Based Convex Trigonal-Prismatic Cages via Coordination-Driven Self-Assembly and C60 Encapsulation. , 2017, Inorganic chemistry.

[8]  J. F. Stoddart,et al.  Mechanical-Bond-Protected, Air-Stable Radicals. , 2017, Journal of the American Chemical Society.

[9]  Michael T. Otley,et al.  An efficient artificial molecular pump , 2017 .

[10]  Jeremy K M Sanders,et al.  Selective C70 encapsulation by a robust octameric nanospheroid held together by 48 cooperative hydrogen bonds , 2017, Nature Communications.

[11]  H. Isobe,et al.  Entropy-Driven Ball-in-Bowl Assembly of Fullerene and Geodesic Phenylene Bowl. , 2017, Organic letters.

[12]  V. Lynch,et al.  Expanded Rosarin: A Versatile Fullerene (C60) Receptor. , 2017, Journal of the American Chemical Society.

[13]  Q. Guo,et al.  O6-Corona[6]arenes with Expanded Cavities for Specific Complexation with C70. , 2017, Organic letters.

[14]  Ryan M. Young,et al.  Intramolecular Energy and Electron Transfer within a Diazaperopyrenium-Based Cyclophane. , 2017, Journal of the American Chemical Society.

[15]  J. F. Stoddart,et al.  Size-Matched Radical Multivalency. , 2017, Journal of the American Chemical Society.

[16]  Peyman Z. Moghadam,et al.  A Redox-Active Bistable Molecular Switch Mounted inside a Metal-Organic Framework. , 2016, Journal of the American Chemical Society.

[17]  Stefano Artin Serapian,et al.  Molecular Basis for the Recognition of Higher Fullerenes into Ureidopyrimidinone-Cyclotriveratrylene Self-Assembled Capsules. , 2016, Chemistry.

[18]  J. C. Barnes,et al.  Influence of Constitution and Charge on Radical Pairing Interactions in Tris-radical Tricationic Complexes. , 2016, Journal of the American Chemical Society.

[19]  Severin T. Schneebeli,et al.  Cooperative Reactivity in an Extended-Viologen-Based Cyclophane. , 2016, Journal of the American Chemical Society.

[20]  Nicolaas A. Vermeulen,et al.  Supramolecular Explorations: Exhibiting the Extent of Extended Cationic Cyclophanes. , 2016, Accounts of chemical research.

[21]  Nicolaas A. Vermeulen,et al.  Catenation through a Combination of Radical Templation and Ring-Closing Metathesis. , 2015, Journal of the American Chemical Society.

[22]  P. Erhart,et al.  High‐Entropy Mixtures of Pristine Fullerenes for Solution‐Processed Transistors and Solar Cells , 2015, Advanced materials.

[23]  Nicolaas A. Vermeulen,et al.  Allosteric Modulation of Substrate Binding within a Tetracationic Molecular Receptor. , 2015, Journal of the American Chemical Society.

[24]  J. F. Stoddart,et al.  Redox Control of the Binding Modes of an Organic Receptor. , 2015, Journal of the American Chemical Society.

[25]  Hao Li,et al.  An artificial molecular pump. , 2015, Nature nanotechnology.

[26]  L. García-Escudero,et al.  Assembling nonplanar polyaromatic units by click chemistry. Study of multicorannulene systems as host for fullerenes. , 2015, Organic letters.

[27]  J. C. Barnes,et al.  Semiconducting single crystals comprising segregated arrays of complexes of C60. , 2015, Journal of the American Chemical Society.

[28]  Nicolaas A. Vermeulen,et al.  Modulating the binding of polycyclic aromatic hydrocarbons inside a hexacationic cage by anion-π interactions. , 2014, Angewandte Chemie.

[29]  Sílvia Osuna,et al.  Sponge-like molecular cage for purification of fullerenes , 2014, Nature Communications.

[30]  Yinghua Jin,et al.  A tetrameric cage with D2h symmetry through alkyne metathesis. , 2014, Angewandte Chemie.

[31]  Ryan M. Young,et al.  Solid-state characterization and photoinduced intramolecular electron transfer in a nanoconfined octacationic homo[2]catenane. , 2014, Journal of the American Chemical Society.

[32]  J. O. Jeppesen,et al.  Ion-regulated allosteric binding of fullerenes (C60 and C70) by tetrathiafulvalene-calix[4]pyrroles. , 2014, Journal of the American Chemical Society.

[33]  Severin T. Schneebeli,et al.  Redox switchable daisy chain rotaxanes driven by radical-radical interactions. , 2014, Journal of the American Chemical Society.

[34]  Takashi Nakamura,et al.  A C60-templated tetrameric porphyrin barrel complex via zinc-mediated self-assembly utilizing labile capping ligands. , 2013, Journal of the American Chemical Society.

[35]  Ryan M. Young,et al.  Relative unidirectional translation in an artificial molecular assembly fueled by light. , 2013, Journal of the American Chemical Society.

[36]  Nicolaas A. Vermeulen,et al.  Synthesis of Ex(n)Box cyclophanes. , 2013, The Journal of organic chemistry.

[37]  Peter D. Frischmann,et al.  Giant electroactive M4L6 tetrahedral host self-assembled with Fe(II) vertices and perylene bisimide dye edges. , 2013, Journal of the American Chemical Society.

[38]  S. Hayashi,et al.  Facile catch and release of fullerenes using a photoresponsive molecular tube. , 2013, Journal of the American Chemical Society.

[39]  D. Guldi,et al.  Host-guest complexation of [60]fullerenes and porphyrins enabled by "click chemistry". , 2013, Chemistry.

[40]  D. Dougherty.  The cation-π interaction. , 2013, Accounts of chemical research.

[41]  J. Lehn.  Perspectives in chemistry--steps towards complex matter. , 2013, Angewandte Chemie.

[42]  Chien‐Chen Lai,et al.  Hemicarceplex formation with a cyclotriveratrylene-based molecular cage allows isolation of high-purity (≥99.0%) C70 directly from fullerene extracts. , 2012, Organic letters.

[43]  T. Torres,et al.  Towards artificial photosynthesis: Supramolecular, donor–acceptor, porphyrin- and phthalocyanine/carbon nanostructure ensembles , 2012 .

[44]  A. Seitsonen,et al.  Selective supramolecular fullerene-porphyrin interactions and switching in surface-confined C60-Ce(TPP)2 dyads. , 2012, Nano letters.

[45]  Yoshiharu Sato,et al.  An Amorphous Mesophase Generated by Thermal Annealing for High‐Performance Organic Photovoltaic Devices , 2012, Advanced materials.

[46]  J. C. Barnes,et al.  Mechanically induced intramolecular electron transfer in a mixed-valence molecular shuttle , 2012, Proceedings of the National Academy of Sciences.

[47]  M. Sallé,et al.  A BPTTF-based self-assembled electron-donating triangle capable of C60 binding. , 2012, Chemical communications.

[48]  Zhijuan Zhang,et al.  A multifunctional organic-inorganic hybrid structure based on Mn(III)-porphyrin and polyoxometalate as a highly effective dye scavenger and heterogenous catalyst. , 2012, Journal of the American Chemical Society.

[49]  Frank Neese,et al.  The ORCA program system , 2012 .

[50]  Wei Zhang,et al.  A highly C70 selective shape-persistent rectangular prism constructed through one-step alkyne metathesis. , 2011, Journal of the American Chemical Society.

[51]  Stefan Grimme,et al.  Effect of the damping function in dispersion corrected density functional theory , 2011, J. Comput. Chem..

[52]  K. Rissanen,et al.  A self-assembled M8L6 cubic cage that selectively encapsulates large aromatic guests. , 2011, Angewandte Chemie.

[53]  D. Guldi,et al.  A new exTTF-crown ether platform to associate fullerenes: cooperative n-π and π-π effects. , 2010, Journal of the American Chemical Society.

[54]  N. Aratani,et al.  A porphyrin nanobarrel that encapsulates C(60). , 2010, Journal of the American Chemical Society.

[55]  M. Fujita,et al.  Networked molecular cages as crystalline sponges for fullerenes and other guests. , 2010, Nature chemistry.

[56]  J. Morton,et al.  A cyclic porphyrin trimer as a receptor for fullerenes. , 2010, Organic letters.

[57]  M. Mastalerz.  Shape-persistent organic cage compounds by dynamic covalent bond formation. , 2010, Angewandte Chemie.

[58]  Chuan-feng Chen,et al.  Triptycene-derived oxacalixarene with expanded cavity: synthesis, structure and its complexation with fullerenes C60 and C70. , 2010, Chemical communications.

[59]  S. Grimme,et al.  A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. , 2010, The Journal of chemical physics.

[60]  N. Martín,et al.  Tripodal exTTF-CTV hosts for fullerenes. , 2010, Journal of the American Chemical Society.

[61]  Pei-Jung Li,et al.  Highly efficient and stable inverted polymer solar cells integrated with a cross-linked fullerene material as an interlayer. , 2010, Journal of the American Chemical Society.

[62]  E. Ortí,et al.  A bis-exTTF macrocyclic receptor that associates C60 with micromolar affinity. , 2010, Journal of the American Chemical Society.

[63]  Shijun Jia,et al.  Polymer–Fullerene Bulk‐Heterojunction Solar Cells , 2009, Advanced materials.

[64]  Craig J. Medforth,et al.  Self-assembled porphyrin nanostructures. , 2009, Chemical communications.

[65]  J. F. Stoddart,et al.  The chemistry of the mechanical bond. , 2009, Chemical Society reviews.

[66]  A. Tsivadze,et al.  Supramolecular chemistry of metalloporphyrins. , 2009, Chemical reviews.

[67]  Ivana Radivojevic,et al.  Self-organized porphyrinic materials. , 2009, Chemical reviews.

[68]  P. Mal,et al.  Supramolecular multicomponent self-assembly of shape-adaptive nanoprisms: wrapping up C(60) with three porphyrin units. , 2008, Organic letters.

[69]  J. Sanders,et al.  Supramolecular assemblies of tripodal porphyrin hosts and C60. , 2008, Chemistry.

[70]  D. Truhlar,et al.  The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals , 2008 .

[71]  A. Fragoso,et al.  Selective binding and easy separation of C70 by nanoscale self-assembled capsules. , 2007, Angewandte Chemie.

[72]  F. Giacalone,et al.  Fullerene polymers: synthesis and properties. , 2006, Chemical reviews.

[73]  J. Hummelen,et al.  Air‐Stable n‐Channel Organic Transistors Based on a Soluble C84 Fullerene Derivative , 2006 .

[74]  L. Sánchez,et al.  exTTF as a building block for fullerene receptors. unexpected solvent-dependent positive homotropic cooperativity. , 2006, Journal of the American Chemical Society.

[75]  F. Diederich,et al.  A Two‐Dimensional Porphyrin‐Based Porous Network Featuring Communicating Cavities for the Templated Complexation of Fullerenes , 2006 .

[76]  Zhan-Ting Li,et al.  Hydrogen-bonding-driven preorganized zinc porphyrin receptors for efficient complexation of C60, C70, and C60 derivatives. , 2005, Journal of the American Chemical Society.

[77]  C. Reed,et al.  Fullerene-porphyrin constructs. , 2005, Accounts of chemical research.

[78]  T. Aida,et al.  Selective extraction of higher fullerenes using cyclic dimers of zinc porphyrins. , 2004, Journal of the American Chemical Society.

[79]  T. Kawase,et al.  Onion-type complexation based on carbon nanorings and a buckminsterfullerene. , 2004, Angewandte Chemie.

[80]  Meining Wang,et al.  Synthesis, structure, and [60]fullerene complexation properties of azacalix[m]arene[n]pyridines. , 2004, Angewandte Chemie.

[81]  F. Diederich,et al.  Exceptional redox and photophysical properties of a triply fused diporphyrin-C60 conjugate: novel scaffolds for multicharge storage in molecular scale electronics. , 2003, Angewandte Chemie.

[82]  Zhenyang Lin,et al.  Supramolecular interactions between fullerenes and porphyrins. , 2003, Journal of the American Chemical Society.

[83]  F. Tham,et al.  Supramolecular fullerene-porphyrin chemistry. Fullerene complexation by metalated "jaws porphyrin" hosts. , 2002, Journal of the American Chemical Society.

[84]  S. Shinkai,et al.  A novel [60]fullerene receptor with a Pd(II)-switched bisporphyrin cleft. , 2002, Chemical communications.

[85]  Jean-Marie Lehn,et al.  Toward Self-Organization and Complex Matter , 2002, Science.

[86]  Christopher A. Reed,et al.  Porphyrin-fullerene host-guest chemistry , 2000 .

[87]  Takuzo Aida,et al.  A Cyclic Dimer of Metalloporphyrin Forms a Highly Stable Inclusion Complex with C60 , 1999 .

[88]  V. Barone,et al.  Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model , 1998 .

[89]  D. A. Dougherty,et al.  The Cationminus signpi Interaction. , 1997, Chemical reviews.

[90]  George A. Koutsantonis,et al.  Purification of C60 and C70 by selective complexation with calixarenes , 1994, Nature.

[91]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[92]  B. Meunier.  Metalloporphyrins as versatile catalysts for oxidation reactions and oxidative DNA cleavage , 1992 .

[93]  D. Bethune,et al.  Fullerene Structure and Dynamics: A Magnetic Resonance Potpourri , 1992 .

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

[95]  W. Krätschmer,et al.  Solid C60: a new form of carbon , 1990, Nature.

[96]  Jean-Marie Lehn,et al.  Supramolecular Chemistry—Scope and Perspectives Molecules, Supermolecules, and Molecular Devices (Nobel Lecture) , 1988 .

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