Synthesis of trans‐A2B2‐ and trans‐A2BC‐Porphyrins with Polar 4′‐(Dimethylamino)tolan‐4‐yl Substituents, and a Screening Protocol for Vapor‐Phase Deposition on Metal Surfaces

The role of polar 4-[p-(dimethylamino) phenylethynyl] phenyl substituents, with a calculated dipole moment of 3.35 Debye, in the self-assembly of trans-A(2)B(2)- and A(2)BC-substituted porphyrins was explored in the solid state by X-ray crystallography, and on an Au(111) surface by scanning tunneling microscopy (STM). Our results demonstrate that the dipolar character of these substituents blocks the 2D self-assembly of porphyrins into larger ordered domains on Au(111) at low coverage, whereas antiparallel dipole-dipole interactions govern the molecular ordering in the crystal. The STM analysis revealed an adaptation of the conformation of the prochiral building blocks and a site-selectivity of the adsorption. We present a general protocol for testing the suitability of higher-molecular-weight compounds, such as porphyrins, to be deposited on surface by sublimation in ultra-high vacuum (UHV). This protocol combines classical methods of chemical analysis with typical surface science techniques.

[1]  Hannes Hahne,et al.  A hydrodynamically optimized nano-electrospray ionization source and vacuum interface. , 2014, The Analyst.

[2]  Suhrit Ghosh,et al.  Supramolecular assemblies by charge-transfer interactions between donor and acceptor chromophores. , 2014, Angewandte Chemie.

[3]  F. Diederich,et al.  Cyanobuta-1,3-dienes as novel electron acceptors for photoactive multicomponent systems. , 2014, Chemistry.

[4]  H. Fuchs,et al.  Glaser coupling at metal surfaces. , 2013, Angewandte Chemie.

[5]  W. Heckl,et al.  On-surface polymerization of 1,4-diethynylbenzene on Cu(111). , 2013, Chemical communications.

[6]  P. Liu,et al.  Steering on-surface polymerization with metal-directed template. , 2013, Journal of the American Chemical Society.

[7]  F. Besenbacher,et al.  On-surface azide-alkyne cycloaddition on Cu(111): does it "click" in ultrahigh vacuum? , 2013, Journal of the American Chemical Society.

[8]  Timothy R. Cook,et al.  Metal-organic frameworks and self-assembled supramolecular coordination complexes: comparing and contrasting the design, synthesis, and functionality of metal-organic materials. , 2013, Chemical reviews.

[9]  M. Milčić,et al.  CH/π interactions in metal-porphyrin complexes with pyrrole and chelate rings as hydrogen acceptors. , 2012, Journal of inorganic biochemistry.

[10]  F. Diederich,et al.  Controlling the dimensionality and structure of supramolecular porphyrin assemblies by their functional substituents: dimers, chains, and close-packed 2D assemblies. , 2012, Chemistry.

[11]  Shuichi Suzuki,et al.  Construction of snowflake-shaped dendritic covalent assemblies with rigid conjugated networks. , 2012, The Journal of organic chemistry.

[12]  B. Mishra,et al.  Tuning the C-H···π Interaction by Different Substitutions in Benzene-Acetylene Complexes. , 2012, Journal of chemical theory and computation.

[13]  S. Hecht,et al.  Controlling on-surface polymerization by hierarchical and substrate-directed growth. , 2012, Nature chemistry.

[14]  Laura Maggini,et al.  Hierarchised luminescent organic architectures: design, synthesis, self-assembly, self-organisation and functions. , 2012, Chemical Society reviews.

[15]  R. Miranda,et al.  Molecular Self‐Assembly at Solid Surfaces , 2011, Advanced materials.

[16]  Paul Seiler,et al.  Regular acyclic and macrocyclic [AB] oligomers by formation of push-pull chromophores in the chain-growth step. , 2011, Chemistry.

[17]  F. Diederich,et al.  Visualizing the product of a formal cycloaddition of 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) to an acetylene-appended porphyrin by scanning tunneling microscopy on Au(111). , 2011, Chemistry.

[18]  J. Steed.  Supramolecular gel chemistry: developments over the last decade. , 2011, Chemical communications.

[19]  J. Otsuki.  STM studies on porphyrins , 2010 .

[20]  D. Bonifazi,et al.  Supramolecular architectures of porphyrins on surfaces: The structural evolution from 1D to 2D to 3D to devices , 2010 .

[21]  J. Barth,et al.  Hierarchic self-assembly of nanoporous chiral networks with conformationally flexible porphyrins. , 2010, ACS nano.

[22]  Shuguang Zhang,et al.  Designer self-assembling peptide nanofiber biological materials. , 2010, Chemical Society reviews.

[23]  F. Diederich,et al.  Two-dimensional phase behavior of a bimolecular porphyrin system at the solid-vacuum interface. , 2010, Journal of the American Chemical Society.

[24]  J. Barth,et al.  Self-assembly of flexible one-dimensional coordination polymers on metal surfaces. , 2010, Journal of the American Chemical Society.

[25]  Timur K. Kim,et al.  Self-Assembly and Superexchange Coupling of Magnetic Molecules on Oxygen-Reconstructed Ferromagnetic Thin Film , 2010 .

[26]  Yanchun Han,et al.  Active and responsive polymer surfaces. , 2010, Chemical Society reviews.

[27]  N. Lin,et al.  Self-assembly of a two-dimensional bimetallic coordination framework and dynamic control of reversible conversions to homo-metallic hydrogen-bond arrays. , 2010, Chemphyschem : a European journal of chemical physics and physical chemistry.

[28]  J. Barth,et al.  Surface-assisted assembly of discrete porphyrin-based cyclic supramolecules. , 2010, Nano letters.

[29]  K. Kern,et al.  Electrospray ion beam deposition: soft-landing and fragmentation of functional molecules at solid surfaces. , 2009, ACS nano.

[30]  D. Bonifazi,et al.  Supramolecular chemistry at interfaces: molecular recognition on nanopatterned porous surfaces. , 2009, Chemistry.

[31]  S. De Feyter,et al.  Two-dimensional supramolecular self-assembly: nanoporous networks on surfaces. , 2009, Chemical Society reviews.

[32]  F. Diederich,et al.  Probing hydrogen bonding to bound dioxygen in synthetic models for heme proteins: the importance of precise geometry. , 2009, Chemistry.

[33]  J. Lindsey,et al.  Investigation of the scope of a new route to ABCD-bilanes and ABCD-porphyrins. , 2008, The Journal of organic chemistry.

[34]  J. Lindsey,et al.  Rational or statistical routes from 1-acyldipyrromethanes to meso-substituted porphyrins. Distinct patterns, multiple pyridyl substituents, and amphipathic architectures. , 2008, The Journal of organic chemistry.

[35]  F. Diederich,et al.  Supramolecular synthons on surfaces: controlling dimensionality and periodicity of tetraarylporphyrin assemblies by the interplay of cyano and alkoxy substituents. , 2008, Chemistry.

[36]  N. Miyashita,et al.  Directing supramolecular assemblies on surfaces , 2008 .

[37]  R. Miranda,et al.  Molecular Conformation, Organizational Chirality, and Iron Metalation of meso-Tetramesitylporphyrins on Copper(100) , 2008 .

[38]  T. Jung,et al.  Two-Dimensional Multiphase Behavior Induced by Sterically Hindered Conformational Optimization of Phenoxy-Substituted Phthalocyanines , 2008 .

[39]  F. Diederich,et al.  Direct evidence for a hydrogen bond to bound dioxygen in a myoglobin/hemoglobin model system and in cobalt myoglobin by pulse-EPR spectroscopy. , 2008, Angewandte Chemie.

[40]  M. Persson,et al.  Nano-architectures by covalent assembly of molecular building blocks. , 2007, Nature nanotechnology.

[41]  Duncan M. Tooke,et al.  One-dimensional, cofacial porphyrin polymers formed by self-assembly of meso-tetrakis(ERE donor) zinc(II) porphyrins. , 2007, Chemistry, an Asian journal.

[42]  F. Diederich,et al.  A supramolecular multiposition rotary device. , 2007, Angewandte Chemie.

[43]  F. Diederich,et al.  Supramolecular Nanostructuring of Silver Surfaces via Self‐Assembly of [60]Fullerene and Porphyrin Modules , 2007 .

[44]  J. Barth,et al.  Molecular architectonic on metal surfaces. , 2007, Annual review of physical chemistry.

[45]  J. Fréchet,et al.  Organic semiconducting oligomers for use in thin film transistors. , 2007, Chemical reviews.

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

[47]  A. Jaworek,et al.  Electrospray droplet sources for thin film deposition , 2007 .

[48]  F. Diederich,et al.  Triply fused Zn(II)-porphyrin oligomers: synthesis, properties, and supramolecular interactions with single-walled carbon nanotubes (SWNTs). , 2006, Chemistry.

[49]  F. Diederich,et al.  Donor-substituted 1,1,4,4-tetracyanobutadienes (TCBDS): new chromophores with efficient intramolecular charge-transfer interactions by atom-economic synthesis. , 2006, Chemistry.

[50]  K. Kern,et al.  Engineering atomic and molecular nanostructures at surfaces , 2005, Nature.

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

[52]  J. Lindsey,et al.  Direct synthesis of palladium porphyrins from acyldipyrromethanes. , 2005, The Journal of organic chemistry.

[53]  S. Buchwald,et al.  Catalysts for Suzuki-Miyaura coupling processes: scope and studies of the effect of ligand structure. , 2005, Journal of the American Chemical Society.

[54]  Ivan Biaggio,et al.  A new class of organic donor-acceptor molecules with large third-order optical nonlinearities. , 2005, Chemical communications.

[55]  F. Diederich,et al.  Synthesis of Dendritic Metalloporphyrins with Distal H-Bond Donors as Model Systems for Hemoglobin , 2005 .

[56]  S. Mashiko,et al.  Conformation selective assembly of carboxyphenyl substituted porphyrins on Au (111). , 2004, The Journal of chemical physics.

[57]  Stephen R. Forrest,et al.  The path to ubiquitous and low-cost organic electronic appliances on plastic , 2004, Nature.

[58]  K. Schulten,et al.  Molecular biomimetics: nanotechnology through biology , 2003, Nature materials.

[59]  T. Steiner.  The hydrogen bond in the solid state. , 2002, Angewandte Chemie.

[60]  F. Diederich,et al.  Dendritic Iron(II) Porphyrins as Models for Hemoglobin and Myoglobin: Specific Stabilization of O2 Complexes in Dendrimers with H-Bond-Donor Centers , 2002 .

[61]  Shiyoshi Yokoyama,et al.  Selective assembly on a surface of supramolecular aggregates with controlled size and shape , 2001, Nature.

[62]  S. Mashiko,et al.  Nonplanar adsorption and orientational ordering of porphyrin molecules on Au(111) , 2001 .

[63]  D L Taylor,et al.  Real-time molecular and cellular analysis: the new frontier of drug discovery. , 2001, Current opinion in biotechnology.

[64]  R. Wagner,et al.  Structural Control of Photoinduced Energy Transfer between Adjacent and Distant Sites in Multiporphyrin Arrays , 2000 .

[65]  Roos,et al.  Synthesis of 3,5-disubstituted 4-hydroxybenzoates by aryl-aryl and alkynyl-aryl coupling , 2000, The Journal of organic chemistry.

[66]  L. S. Liebeskind,et al.  3-Cyclobutenyl-1,2-dione-substituted porphyrins. A general and efficient entry to porphyrin-quinone and quinone-porphyrin-quinone architectures. , 2000, The Journal of organic chemistry.

[67]  D. Mansuy,et al.  A new general method for selective β-polynitrationof porphyrins; preparation and redox properties of Zn-porphyrins bearingone through to eight β-nitro substituents and X-ray structure of thefirst Zn β-pernitro porphyrin , 2000 .

[68]  Diederich,et al.  Dendritic Iron Porphyrins with Tethered Axial Ligands: New Model Compounds for Cytochromes. , 1999, Angewandte Chemie.

[69]  R. Wagner,et al.  Investigation and Refinement of Palladium-Coupling Conditions for the Synthesis of Diarylethyne-Linked Multiporphyrin Arrays , 1999 .

[70]  W. Scheidt,et al.  Structure and Apparent Reactivity of the pi-Cation Radical Derivatives of Zinc and Copper 5,10,15,20-Tetra(2,6-dichlorophenyl)porphyrinate. , 1999, Inorganic chemistry.

[71]  M. Therien,et al.  Suzuki Porphyrins: New Synthons for the Fabrication of Porphyrin-Containing Supramolecular Assemblies , 1998 .

[72]  D. Braga,et al.  X−H---π (X = O, N, C) Hydrogen Bonds in Organometallic Crystals , 1998 .

[73]  M. Nishio,et al.  CH/π Interaction in the Crystal Structure of Organic Compounds. A Database Study , 1998 .

[74]  H. Masuda,et al.  Self-Assembly of Porphyrin Arrays by Hydrogen Bonding in the Solid State: An Orthogonal Porphyrin–Bisresorcinol System , 1998 .

[75]  I. Goldberg,et al.  Supramolecular Multiporphyrin Architecture. Coordination Polymers and Open Networks in Crystals of Tetrakis(4-cyanophenyl)- and Tetrakis(4-nitrophenyl)metalloporphyrin. , 1998, Inorganic chemistry.

[76]  T. Wallow,et al.  Mechanistic Studies on the Aryl−Aryl Interchange Reaction of ArPdL2I (L = Triarylphosphine) Complexes , 1997 .

[77]  J. K. Gimzewski,et al.  Conformational identification of individual adsorbed molecules with the STM , 1997, Nature.

[78]  M. Therien,et al.  Exceptional electronic modulation of porphyrins through meso-arylethynyl groups. Electronic spectroscopy, electronic structure, and electrochemistry of [5,15-bis](aryl)ethynyl]-10,20-diphenylporphinato]zinc(II) complexes , 1996 .

[79]  Y. Hsiou,et al.  Porphyrin sponges: conservative of host structure in over 200 porphyrin-based lattice clathrates , 1993 .

[80]  Ertl,et al.  Scanning tunneling microscopy observations on the reconstructed Au(111) surface: Atomic structure, long-range superstructure, rotational domains, and surface defects. , 1990, Physical review. B, Condensed matter.

[81]  S. Eaton,et al.  Crystal and molecular structure of a six-coordinate zinc porphyrin: Bis(tetrahydrofuran)(5,10,15,20-tetraphenylporphinato)zinc(II) , 1985 .

[82]  C. Glaser.  Beiträge zur Kenntniss des Acetenylbenzols , 1869 .

[83]  C. Glaser.  Untersuchungen über einige Derivate der Zimmtsäure , 1867 .