Porphyrins and other tetrapyrrole macrocycles possess an impressive variety of functional properties that have been exploited in natural and artificial systems. Different metal centres incorporated within the tetradentate ligand are key for achieving and regulating vital processes, including reversible axial ligation of adducts, electron transfer, light-harvesting and catalytic transformations. Tailored substituents optimize their performance, dictating their arrangement in specific environments and mediating the assembly of molecular nanoarchitectures. Here we review the current understanding of these species at well-defined interfaces, disclosing exquisite insights into their structural and chemical properties, and also discussing methods by which to manipulate their intramolecular and organizational features. The distinct characteristics arising from the interfacial confinement offer intriguing prospects for molecular science and advanced materials. We assess the role of surface interactions with respect to electronic and physicochemical characteristics, and describe in situ metallation pathways, molecular magnetism, rotation and switching. The engineering of nanostructures, organized layers, interfacial hybrid and bio-inspired systems is also addressed.
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Küster, W. Beiträge zur Kenntnis des Bilirubins und Hämins. Hoppe-Seyler´s Z. Physiol. Chem. 82, 463–483 (1912).
Battersby, A. R. Tetrapyrroles: The pigments of life. Nat. Prod. Rep. 17, 507–526 (2000).
Ghosh, A. First-principles quantum chemical studies of porphyrins. Acc. Chem. Res. 31, 189–198 (1998).
Hodgson, G. W. & Baker, B. L. Porphyrin abiogenesis from pyrrole and formaldehyde under simulated geochemical conditions. Nature 216, 29–32 (1967).
Lindsey, J. S. & Bocian, D. F. Molecules for charge-based information storage. Acc. Chem. Res. 44, 638–650 (2011).
Bechet, D. et al. Nanoparticles as vehicles for delivery of photodynamic therapy agents. Trends Biotechnol. 26, 612–621 (2008).
Yella, A. et al. Porphyrin-sensitized solar cells with cobalt (II/III)-based redox electrolyte exceed 12 percent efficiency. Science 334, 629–634 (2011).
Jung, T., Schlittler, R. & Gimzewski, J. Conformational identification of individual adsorbed molecules with the STM. Nature 386, 696–698 (1997).
Yokoyama, T., Yokoyama, S., Kamidado, T. & Mashiko, S. Nonplanar adsorption and orientational ordering of porphyrin molecules on Au(111). J. Chem. Phys. 115, 3814 (2001).
Kuck, S. et al. “Naked” iron-5, 10, 15-triphenylcorrole on Cu(111): Observation of chirality on a surface and manipulation of multiple conformational states by STM. J. Am. Chem. Soc. 130, 14072–14073 (2008).
Rosa, A., Ricciardi, G. & Baerends, E. J. Synergism of porphyrin-core saddling and twisting of meso-aryl substituents. J. Phys. Chem. A 110, 5180–5190 (2006).
Moresco, F. et al. Conformational changes of single molecules induced by scanning tunneling microscopy manipulation: A route to molecular switching. Phys. Rev. Lett. 86, 672–675 (2001).
Auwärter, W. et al. Self-assembly and conformation of tetrapyridyl-porphyrin molecules on Ag(111). J. Chem. Phys. 124, 194708–194706 (2006).
Auwärter, W. et al. Conformational adaptation and selective adatom capturing of tetrapyridyl-porphyrin molecules on a copper (111) surface. J. Am. Chem. Soc. 129, 11279–11285 (2007).
Wölfle, T., Görling, A. & Hieringer, W. Conformational flexibility of metalloporphyrins studied by density-functional calculations. Phys. Chem. Chem. Phys. 10, 5739–5742 (2008).
Loppacher, C. et al. Direct determination of the energy required to operate a single molecule switch. Phys. Rev. Lett. 90, 066107 (2003).
Iancu, V., Deshpande, A. & Hla, S-W. Manipulating Kondo temperature via single molecule switching. Nano Lett. 6, 820–823 (2006).
Auwärter, W. et al. Controlled metalation of self-assembled porphyrin nanoarrays in two dimensions. ChemPhysChem 8, 250–254 (2007).
de Jong, M. P. et al. Orbital-specific dynamic charge transfer from Fe(II)-tetraphenylporphyrin molecules to molybdenum disulfide substrates. Phys. Rev. B 72, 035448 (2005).
Weber-Bargioni, A. et al. Visualizing the frontier orbitals of a conformationally adapted metalloporphyrin. ChemPhysChem 9, 89–94 (2008).
Klappenberger, F. et al. Temperature dependence of conformation, chemical state, and metal-directed assembly of tetrapyridyl-porphyrin on Cu(111). J. Chem. Phys. 129, 214702 (2008).
Auwärter, W. et al. Site-specific electronic and geometric interface structure of Co-tetraphenyl-porphyrin layers on Ag(111). Phys. Rev. B 81, 245403 (2010).
Diller, K. et al. Self-metalation of 2H-tetraphenylporphyrin on Cu(111): An X-ray spectroscopy study. J. Chem. Phys. 136, 014705–014713 (2012).
Bischoff, F. et al. How surface bonding and repulsive interactions cause phase transformations: Ordering of a prototype macrocyclic compound on Ag(111). ACS Nano 7, 3139–3149 (2013).
Papageorgiou, A. C. et al. Self-terminating protocol for an interfacial complexation reaction in vacuo by metal–organic chemical vapor deposition. ACS Nano 7, 4520–4526 (2013).
Donovan, P., Robin, A., Dyer, M., Persson, M. & Raval, R. Unexpected deformations induced by surface interaction and chiral self-assembly of CoII-tetraphenylporphyrin (Co-TPP) adsorbed on Cu(110): A combined STM and periodic DFT study. Chem. Eur. J. 16, 11498 (2010).
Seufert, K. et al. Cis-dicarbonyl binding at cobalt and iron porphyrins with saddle-shape conformation. Nature Chem. 3, 114–119 (2011).
Di Santo, G. et al. Conformational adaptation and electronic structure of 2H-tetraphenylporphyrin on Ag(111) during Fe metalation. J. Phys. Chem. C 115, 4155–4162 (2011).
Heim, D. et al. Self-assembly of flexible one-dimensional coordination polymers on metal surfaces. J. Am. Chem. Soc. 132, 6783–6790 (2010).
Heim, D. et al. Surface-assisted assembly of discrete porphyrin-based cyclic supramolecules. Nano Lett. 10, 122–128 (2009).
Écija, D. et al. Hierarchic self-assembly of nanoporous chiral networks with conformationally flexible porphyrins. ACS Nano 4, 4936–4942 (2010).
Lukasczyk, T. et al. Interaction of cobalt(II) tetraaryporphyrins with a Ag(111) surface studied with photoelectron spectroscopy. J. Phys. Chem. C 111, 3090–3098 (2007).
Diller, K. et al. Investigating the molecule-substrate interaction of prototypic tetrapyrrole compounds: Adsorption and self-metalation of porphine on Cu(111). J. Chem. Phys. 138, 154710–154719 (2013).
Scudiero, L., Barlow, D. E., Mazur, U. & Hipps, K. W. Scanning tunneling microscopy, orbital-mediated tunneling spectroscopy, and ultraviolet photoelectron spectroscopy of metal(II) tetraphenylporphyrins deposited from vapor. J. Am. Chem. Soc. 123, 4073–4080 (2001).
Scudiero, L., Barlow, D. E. & Hipps, K. W. Physical properties and metal ion specific scanning tunneling microscopy images of metal (II) tetraphenylporphyrins deposited from vapor onto gold (111). J. Phys. Chem. B 104, 11899–11905 (2000).
Buchner, F. et al. Chemical fingerprints of large organic molecules in scanning tunneling microscopy: Imaging adsorbate-substrate coupling of metalloporphyrins. J. Phys. Chem. C 113, 16450–16457 (2009).
Haq, S. et al. Clean coupling of unfunctionalized porphyrins at surfaces to give highly oriented organometallic oligomers. J. Am. Chem. Soc. 133, 12031–12039 (2011).
Komeda, T. et al. Observation and electric current control of a local spin in a single-molecule magnet. Nature Commun. 2, 217 (2011).
Robles, R. et al. Spin doping of individual molecules by using single-atom manipulation. Nano Lett. 12, 3609–3612 (2012).
Scheybal, A. et al. Induced magnetic ordering in a molecular monolayer. Chem. Phys. Lett. 4, 214–220 (2005).
Bhandary, S. et al. Manipulation of spin state of iron porphyrin by chemisorption on magnetic substrates. Phys. Rev. B 88, 024401 (2013).
Wende, H. et al. Substrate-induced magnetic ordering and switching of iron porphyrin molecules. Nature Mater. 6, 516–520 (2007).
Bernien, M. et al. Tailoring the nature of magnetic coupling of Fe-porphyrin molecules to ferromagnetic substrates. Phys. Rev. Lett. 102, 047202 (2009).
Stepanow, S. et al. Mixed-valence behavior and strong correlation effects of metal phthalocyanines adsorbed on metals. Phys. Rev. B 83, 220401 (2011).
Heinrich, B. W., Braun, L., Pascual, J. I. & Franke, K. J. Protection of excited spin states by a superconducting energy gap. Nature Phys. 9, 765–768 (2013).
Bhandary, S. et al. Graphene as a reversible spin manipulator of molecular magnets. Phys. Rev. Lett. 107, 257202 (2011).
Lippel, P. H., Wilson, R. J., Miller, M. D., Wöll, C. & Chiang, S. High-resolution imaging of copper-phthalocyanine by scanning-tunneling microscopy. Phys. Rev. Lett. 62, 171–174 (1989).
Liljeroth, P., Repp, J. & Meyer, G. Current-induced hydrogen tautomerization and conductance switching of naphthalocyanine molecules. Science 317, 1203–1206 (2007).
Mohn, F., Gross, L., Moll, N. & Meyer, G. Imaging the charge distribution within a single molecule. Nature Nanotech. 7, 227–231 (2012).
Zhang, R. et al. Chemical mapping of a single molecule by plasmon-enhanced Raman scattering. Nature 498, 82–86 (2013).
Qiu, X. H., Nazin, G. V. & Ho, W. Vibrationally resolved fluorescence excited with submolecular precision. Science 299, 542–546 (2003).
Chen, C., Chu, P., Bobisch, C. A., Mills, D. L. & Ho, W. Viewing the interior of a single molecule: Vibronically resolved photon imaging at submolecular resolution. Phys. Rev. Lett. 105, 217402 (2010).
Eichberger, M. et al. Dimerization boosts one-dimensional mobility of conformationally adapted porphyrins on a hexagonal surface atomic lattice. Nano Lett. 8, 4608–4613 (2008).
Buchner, F. et al. Diffusion, rotation, and surface chemical bond of individual 2H-tetraphenylporphyrin molecules on Cu(111). J. Phys. Chem. C 115, 24172–24177 (2011).
Wintjes, N. et al. A supramolecular multiposition rotary device. Angew. Chem. Int. Ed. 46, 4089–4092 (2007).
Écija, D. et al. Assembly and manipulation of rotatable cerium porphyrinato sandwich complexes on a surface. Angew. Chem. Int. Ed. 50, 3872–3877 (2011).
Tanaka, H. et al. Molecular rotation in self-assembled multidecker porphyrin complexes. ACS Nano 5, 9575–9582 (2011).
Vaughan, O. P. H., Williams, F. J., Bampos, N. & Lambert, R. M. A chemically switchable molecular pinwheel. Angew. Chem. Int. Ed. 45, 3779–3781 (2006).
Qiu, X. H., Nazin, G. V. & Ho, W. Mechanisms of reversible conformational transitions in a single molecule. Phys. Rev. Lett. 93, 196806 (2004).
Auwärter, W. et al. A surface-anchored molecular four-level conductance switch based on single proton transfer. Nature Nanotech. 7, 41–46 (2012).
Kumagai, T. et al. Thermally and vibrationally induced tautomerization of single porphycene molecules on a Cu(110) surface. Phys. Rev. Lett. 111, 246101 (2013).
Kumagai, T. et al. Controlling intramolecular hydrogen transfer in a porphycene molecule with single atoms or molecules located nearby. Nature Chem. 6, 41–46 (2014).
Matino, F. et al. Single azopyridine-substituted porphyrin molecules for configurational and electronic switching. Chem. Commun. 46, 6780–6782 (2010).
Barth, J. V. Fresh perspectives for surface coordination chemistry. Surf. Sci. 603, 1533–1541 (2009).
Wäckerlin, C. et al. Controlling spins in adsorbed molecules by a chemical switch. Nature Commun. 1, 61 (2010).
Wäckerlin, C. et al. Ammonia coordination introducing a magnetic moment in an on-surface low-spin porphyrin. Angew. Chem. Int. Ed. 52, 4568–4571 (2013).
Uhlmann, C., Swart, I. & Repp, J. Controlling the orbital sequence in individual Cu-phthalocyanine molecules. Nano Lett. 13, 777–780 (2013).
Krull, C., Robles, R., Mugarza, A. & Gambardella, P. Site- and orbital-dependent charge donation and spin manipulation in electron-doped metal phthalocyanines. Nature Mater. 12, 337–343 (2013).
Flechtner, K., Kretschmann, A., Steinrück, H-P. & Gottfried, J. M. NO-induced reversible switching of the electronic interaction between a porphyrin-coordinated cobalt ion and a silver surface. J. Am. Chem. Soc. 129, 12110–12111 (2007).
Hieringer, W. et al. The surface trans effect: Influence of axial ligands on the surface chemical bonds of adsorbed metalloporphyrins. J. Am. Chem. Soc. 133, 6206–6222 (2011).
Seufert, K., Auwärter, W. & Barth, J. V. Discriminative response of surface-confined metalloporphyrin molecules to carbon and nitrogen monoxide. J. Am. Chem. Soc. 132, 18141–18146 (2010).
Friesen, B. A., Bhattarai, A., Mazur, U. & Hipps, K. W. Single molecule imaging of oxygenation of cobalt octaethylporphyrin at the solution/solid interface: thermodynamics from microscopy. J. Am. Chem. Soc. 134, 14897–14904 (2012).
den Boer, D. et al. Detection of different oxidation states of individual manganese porphyrins during their reaction with oxygen at a solid/liquid interface. Nature Chem. 5, 621–627 (2013).
Burema, S. R., Seufert, K., Auwärter, W., Barth, J. V. & Bocquet, M-L. Probing nitrosyl ligation of surface-confined metalloporphyrins by inelastic electron tunneling spectroscopy. ACS Nano 7, 5273–5281 (2013).
Qiu, X., Nazin, G. V., Hotzel, A. & Ho, W. Manipulation and characterization of xenon−metalloporphyrin complexation with a scanning tunneling microscope. J. Am. Chem. Soc. 124, 14804–14809 (2002).
Turner, M. et al. Deprotection, tethering, and activation of a one-legged metalloporphyrin on a chemically active metal surface: NEXAFS, synchrotron XPS, and STM study of [SAc]P-Mn(III)Cl on Ag(100). J. Am. Chem. Soc. 131, 14913–14919 (2009).
Berner, S. et al. Activity boost of a biomimetic oxidation catalyst by immobilization onto a gold surface. J. Catal. 244, 86–91 (2006).
Hulsken, B. et al. Real-time single-molecule imaging of oxidation catalysis at a liquid-solid interface. Nature Nanotech. 2, 285–289 (2007).
Xue, T. et al. Graphene-supported hemin as a highly active biomimetic oxidation catalyst. Angew. Chem. Int. Ed. 51, 3822–3825 (2012).
Sedona, F. et al. Tuning the catalytic activity of Ag(110)-supported Fe phthalocyanine in the oxygen reduction reaction. Nature Mater. 11, 970–977 (2012).
Shubina, T. E. et al. Principle and mechanism of direct porphyrin metalation: A joint experimental and theoretical investigation. J. Am. Chem. Soc. 129, 9476–9483 (2007).
Röckert, M. et al. Insights in the reaction mechanistics: Isotopic exchange during the metalation of deuterated tetraphenyl-21, 23D-porphyrin on Cu(111). J. Phys. Chem. C 118, 26729–26736 (2014).
Doyle, C. M. et al. Evidence for the formation of an intermediate complex in the direct metalation of tetra(4-bromophenyl)-porphyrin on the Cu(111) surface. Chem. Commun. 47, 12134–12136 (2011).
Goldoni, A. et al. Room temperature metalation of 2H-TPP monolayer on iron and nickel surfaces by picking up substrate metal atoms. ACS Nano 6, 10800–10807 (2012).
Ditze, S. et al. Activation energy for the self-metalation reaction of 2H-tetraphenylporphyrin on Cu(111). Angew. Chem. Int. Ed. 51, 10898–10901 (2012).
González-Moreno, R. et al. Following the metalation process of protoporphyrin IX with metal substrate atoms at room temperature. J. Phys. Chem. C 115, 6849–6854 (2011).
Rienzo, A. et al. X-ray absorption and photoemission spectroscopy of zinc protoporphyrin adsorbed on rutile TiO2(110) prepared by in situ electrospray deposition. J. Chem. Phys. 132, 084703–084706 (2010).
Barth, J. V. Molecular architectonic on metal surfaces. Annu. Rev. Phys. Chem. 58, 375–407 (2007).
Grill, L. et al. Nano-architectures by covalent assembly of molecular building blocks. Nature Nanotech. 2, 687–691 (2007).
Rojas, G. et al. Self-assembly and properties of nonmetalated tetraphenyl-porphyrin on metal substrates. J. Phys. Chem. C 114, 9408–9415 (2010).
Yokoyama, T., Yokoyama, S., Kamikado, T., Okuno, Y. & Mashiko, S. Selective assembly on a surface of supramolecular aggregates with controlled size and shape. Nature 413, 619–621 (2001).
Wintjes, N. et al. Supramolecular synthons on surfaces: Controlling dimensionality and periodicity of tetraarylporphyrin assemblies by the interplay of cyano and alkoxy substituents. Chem. Eur. J. 14, 5794–5802 (2008).
Yokoyama, T., Kamikado, T., Yokoyama, S. & Mashiko, S. Conformation selective assembly of carboxyphenyl substituted porphyrins on Au (111). J. Chem. Phys. 121, 11993–11997 (2004).
Spillmann, H. et al. A two-dimensional porphyrin-based porous network featuring communicating cavities for the templated complexation of fullerenes. Adv. Mater. 18, 275–279 (2006).
Shi, Z. & Lin, N. Porphyrin-based two-dimensional coordination kagome lattice self-assembled on a Au(111) surface. J. Am. Chem. Soc. 131, 5376–5377 (2009).
Shi, Z. & Lin, N. Structural and chemical control in assembly of multicomponent metal-organic coordination networks on a surface. J. Am. Chem. Soc. 132, 10756–10761 (2010).
Li, Y. et al. Coordination and metalation bifunctionality of Cu with 5, 10, 15, 20-tetra(4-pyridyl)porphyrin: Toward a mixed-valence two-dimensional coordination network. J. Am. Chem. Soc. 134, 6401–6408 (2012).
Fendt, L. et al. Modification of supramolecular binding motifs induced by substrate registry: Formation of self-assembled macrocycles and chain-like patterns. Chem. Eur. J. 15, 11139–11150 (2009).
Hanke, F., Haq, S., Raval, R. & Persson, M. Heat-to-connect: Surface commensurability directs organometallic one-dimensional self-assembly. ACS Nano 5, 9093–9103 (2011).
Adisoejoso, J., Li, Y., Liu, J., Liu, P. N. & Lin, N. Two-dimensional metallo-supramolecular polymerization: Toward size-controlled multi-strand polymers. J. Am. Chem. Soc. 134, 18526–18529 (2012).
Kezilebieke, S., Amokrane, A., Abel, M. & Bucher, J. P. Hierarchy of chemical bonding in the synthesis of Fe-phthalocyanine on metal surfaces: a local spectroscopy approach. J. Phys. Chem. Lett. 5, 3175–3182 (2014).
Nardi, E. et al. On-surface reaction between tetracarbonitrile-functionalized molecules and copper atoms. J. Phys. Chem. C 118, 27549–27553 (2014).
Zhou, J. & Sun, Q. Magnetism of phthalocyanine-based organometallic single porous sheet. J. Am. Chem. Soc. 133, 15113–15119 (2011).
Giovanelli, L. et al. Magnetic coupling and single-ion anisotropy in surface-supported Mn-based metal−organic networks. J. Phys. Chem. C 118, 11738–11744 (2014).
Wiengarten, A. et al. Surface-assisted dehydrogenative homocoupling of porphine molecules. J. Am. Chem. Soc. 136, 9346–9354 (2014).
Lafferentz, L. et al. Controlling on-surface polymerization by hierarchical and substrate-directed growth. Nature Chem. 4, 215–220 (2012).
In't Veld, M., Iavicoli, P., Haq, S., Amabilino, D. B. & Raval, R. Unique intermolecular reaction of simple porphyrins at a metal surface gives covalent nanostructures. Chem. Commun., 1536–1538 (2008).
Haq, S. et al. Versatile bottom-up construction of diverse macromolecules on a surface observed by scanning tunneling microscopy. ACS Nano 9, 8856–8870 (2014).
Shoji, O., Tanaka, H., Kawai, T. & Kobuke, Y. Single molecule visualization of coordination-assembled porphyrin macrocycles reinforced with covalent linkings. J. Am. Chem. Soc. 127, 8598–8599 (2005).
O'Sullivan, M. C. et al. Vernier templating and synthesis of a 12-porphyrin nano-ring. Nature 469, 72–75 (2011).
Mao, J. et al. Tunability of supramolecular kagome lattices of magnetic phthalocyanines using graphene-based moiré patterns as templates. J. Am. Chem. Soc. 131, 14136–14137 (2009).
Joshi, S. et al. Control of molecular organization and energy level alignment by an electronically nanopatterned boron nitride template. ACS Nano 8, 430–442 (2014).
Järvinen, P. et al. Molecular self-assembly on graphene on SiO2 and h-BN substrates. Nano Lett. 13, 3199–3204 (2013).
Bazarnik, M., Brede, J., Decker, R. & Wiesendanger, R. Tailoring molecular self-assembly of magnetic phthalocyanine molecules on Fe- and Co-intercalated graphene. ACS Nano 7, 11341–11349 (2013).
Seufert, K. et al. Controlled interaction of surface quantum-well electronic states. Nano Lett. 13, 6130–6135 (2013).
Qiu, X. et al. Alkane-assisted adsorption and assembly of phthalocyanines and porphyrins. J. Am. Chem. Soc. 122, 5550–5556 (2000).
Lei, S. B. et al. Surface stabilized porphyrin and phthalocyanine two-dimensional network connected by hydrogen bonds. J. Phys. Chem. B 105, 10838–10841 (2001).
Friesen, B. A., Wiggins, B., McHale, J. L., Mazur, U. & Hipps, K. W. Differing HOMO and LUMO mediated conduction in a porphyrin nanorod. J. Am. Chem. Soc. 132, 8554–8556 (2010).
Drain, C. M. et al. Designing supramolecular porphyrin arrays that self-organize into nanoscale optical and magnetic materials. Proc. Natl Acad. Sci. USA 99, 6498–6502 (2002).
Otsuki, J., Komatsu, Y., Kobayashi, D., Asakawa, M. & Miyake, K. Rotational libration of a double-decker porphyrin visualized. J. Am. Chem. Soc. 132, 6870–6871 (2010).
Yoshimoto, S., Sawaguchi, T., Su, W., Jiang, J. & Kobayashi, N. Superstructure formation and rearrangement in the adlayer of a rare-earth-metal triple-decker sandwich complex at the electrochemical interface. Angew. Chem. Int. Ed. 46, 1071–1074 (2007).
van Hameren, R. et al. Macroscopic hierarchical surface patterning of porphyrin trimers via self-assembly and dewetting. Science 314, 1433–1436 (2006).
Sánchez, L., Otero, R., Gallego, J. M., Miranda, R. & Martín, N. Ordering fullerenes at the nanometer scale on solid surfaces. Chem. Rev. 109, 2081–2091 (2009).
Sedona, F. et al. Fullerene/porphyrin multicomponent nanostructures on Ag(110): From supramolecular self-assembly to extended copolymers. ACS Nano 4, 5147–5154 (2010).
Yoshimoto, S., Honda, Y., Ito, O. & Itaya, K. Supramolecular pattern of fullerene on 2D bimolecular chessboard consisting of bottom-up assembly of porphyrin and phthalocyanine molecules. J. Am. Chem. Soc. 130, 1085–1092 (2007).
Bonifazi, D. et al. Supramolecular patterned surfaces driven by cooperative assembly of C60 and porphyrins on metal substrates. Angew. Chem. Int. Ed. 43, 4759–4763 (2004).
Yoshimoto, S. et al. Controlled molecular orientation in an adlayer of a supramolecular assembly consisting of an open-cage C60 derivative and ZnII octaethylporphyrin on Au(111). Angew. Chem. Int. Ed. 43, 3044–3047 (2004).
Vijayaraghavan, S. et al. Selective supramolecular fullerene–porphyrin interactions and switching in surface-confined C60–Ce(TPP)2 dyads. Nano Lett. 12, 4077–4083 (2012).
Bui, P. T., Nishino, T., Yamamoto, Y. & Shiigi, H. Quantitative exploration of electron transfer in a single noncovalent supramolecular assembly. J. Am. Chem. Soc. 135, 5238–5241 (2013).
Ikeda, A., Hatano, T., Shinkai, S., Akiyama, T. & Yamada, S. Efficient photocurrent generation in novel self-assembled multilayers comprised of fullerene-cationic homooxacalixarene inclusion complex and anionic porphyrin polymer J. Am. Chem. Soc. 123, 4855–4956 (2001).
Li, M. et al. Paradigm shift from self-assembly to commanded assembly of functional materials: recent examples in porphyrin/fullerene supramolecular systems. Sci. Technol. Adv. Mater. 13, 053001 (2012).
Takagi, S., Eguchi, M., Tryk, D. A. & Inoue, H. Porphyrin photochemistry in inorganic/organic hybrid materials: Clays, layered semiconductors, nanotubes, and mesoporous materials. J. Photochem. Photobiol. C 7, 104–126 (2006).
Ishida, Y. et al. Efficient excited energy transfer reaction in clay/porphyrin complex toward an artificial light-harvesting system. J. Am. Chem. Soc. 133, 14280–14286 (2011).
Xu, Y. et al. A graphene hybrid material covalently functionalized with porphyrin: Synthesis and optical limiting property. Adv. Mater. 21, 1275–1279 (2009).
Jahan, M., Bao, Q. & Loh, K. P. Electrocatalytically active graphene–porphyrin MOF composite for oxygen reduction reaction. J. Am. Chem. Soc. 134, 6707–6713 (2012).
Malig, J., Jux, N. & Guldi, D. M. Toward multifunctional wet chemically functionalized graphene; integration of oligomeric, molecular, and particulate building blocks that reveal photoactivity and redox activity. Acc. Chem. Res. 46, 53–64 (2013).
Makiura, R. et al. Surface nano-architecture of a metal–organic framework. Nature Mater. 9, 565–571 (2010).
Kay, A. & Grätzel, M. Artificial photosynthesis. 1. Photosensitization of titania solar cells with chlorophyll derivatives and related natural porphyrins. J. Phys. Chem. 97, 6272–6277 (1993).
Boussaad, S., Tazi, A. & Leblanc, R. M. Chlorophyll a dimer: A possible primary electron donor for the photosystem II. Proc. Natl Acad. Sci. USA 94, 3504–3506 (1997).
Iancu, V. & Hla, S-W. Realization of a four-step molecular switch in scanning tunneling microscope manipulation of single chlorohyll-a molecules. Proc. Natl Acad. Sci. USA 103, 13718–13721 (2006).
Balaban, T. S., Tamiaki, H. & Holzwarth, A. R. Chlorins programmed for self-assembly. Top. Curr. Chem. 258, 1–38 (2005).
Sengupta, S. & Würthner, F. Chlorophyll J-aggregates: From bioinspired dye stacks to nanotubes, liquid crystals, and biosupramolecular electronics. Acc. Chem. Res. 46, 2498–2512 (2013).
Sengupta, S. et al. Biosupramolecular nanowires from chlorophyll dyes with exceptional charge-transport properties. Angew. Chem. Int. Ed. 51, 6378–6382 (2012).
Collman, J. P. et al. A cytochrome c oxidase model catalyzes oxygen to water reduction under rate-limiting electron flux. Science 315, 1565–1568 (2007).
Collman, J. P. & Decreau, R. A. Functional biomimetic models for the active site in the respiratory enzyme cytochrome c oxidase. Chem. Commun. 5065–5076 (2008).
Amdursky, N., Pecht, I., Sheves, M. & Cahen, D. Electron transport via cytochrome c on Si–H surfaces: Roles of Fe and heme. J. Am. Chem. Soc. 135, 6300–6306 (2013).
Ricchelli, F. Photophysical properties of porphyrins in biological membranes. J. Photochem. Photobiol. B 29, 109–118 (1995).
Kamat, N. P. et al. Sensing membrane stress with near IR-emissive porphyrins. Proc. Natl Acad. Sci. USA 108, 13984–13989 (2011).
Reeve, J. E. et al. Porphyrins for probing electrical potential across lipid bilayer membranes by second harmonic generation. Angew. Chem. Int. Ed. 52, 9044–9048 (2013).
Kuimova, M. K. et al. Imaging intracellular viscosity of a single cell during photoinduced cell death. Nature Chem. 1, 69–73 (2009).
Lovell, J. F. et al. Porphysome nanovesicles generated by porphyrin bilayers for use as multimodal biophotonic contrast agents. Nature Mater. 10, 324–332 (2011).
Gerster, D. et al. Photocurrent of a single photosynthetic protein. Nature Nanotech. 7, 673–676 (2012).
We are grateful for support from the European Research Council Advanced Grant MolArt (no. 247299), the Munich Centre for Advanced Photonics (MAP) and TUM Institute for Advanced Study funded by the German Research Foundation (DFG) via the German Excellence Initiative, Canadian NSERC and CFI, the Spanish RyC Programme and other funding schemes. We thank all team members and project partners co-authoring cited joint publications.
The authors declare no competing financial interests.
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Auwärter, W., Écija, D., Klappenberger, F. et al. Porphyrins at interfaces. Nature Chem 7, 105–120 (2015). https://doi.org/10.1038/nchem.2159
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