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Supramolecular Structures of Coronene and Alkane Acids at the Au(111)-Solution Interface: a Scanning Tunneling Microscopy Study

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Supramolecular Structures of Coronene and Alkane Acids at the Au(111)-Solution Interface: a Scanning Tunneling Microscopy Study Langmuir 2005, 21, 919-923 919 Supramolecular Structures of Coronene and Alkane Acids at the Au(111)-Solution Interface: A Scanning Tunneling Microscopy Study Brett J. Gyarfas, Bryan Wiggins, Monica Zosel, and K. W. Hipps* Department of Chemistry and Materials Science Program, Washington State University, Pullman, Washington 99164-4630 Received September 11, 2004. In Final Form: October 29, 2004 Scanning tunneling microscopy (STM) is utilized to study the solution-solid interface formed between Au(111) and solutions of coronene in hexanoic, heptanoic, and octanoic acids. In all three cases adsorbed coronene is observed and lays flat on the metal surface. Heptanoic and hexanoic acid solutions produce a hexagonal symmetry monolayer. For the heptanoic and hexanoic cases, dipole-image dipole interactions and H bonding stabilize a surface structure in which 12 acid molecules surround each coronene and produce a coronene spacing of 1.45 nm. In the case of octanoic acid as solvent, the incorporation of the solvent into the monolayer is not as strongly favored. The coronene spacing can range from close-packed (1.2 nm) with no solvent presumed present in the monolayer, to 1.50 nm with up to 12 solvent molecules surrounding each coronene. The close-packed regions have hexagonal symmetry, as do those with the largest (1.5 nm) spacing. Heptanoic acid solutions give the clearest STM images and are associated with the most stable two-component monolayer. The present paper demonstrates that non-covalent interactions at the solution-metal interface can lead to complex multicomponent monolayer structures. Introduction Most recently, the desire to understand the solution- solid interface,17-21 and the design of nanostructures by Supramolecular chemistry is chemistry that uses 22-26 molecules rather than atoms as building blocks. Weak bottom-up methods, has driven the field of supramo- intermolecular forces, not covalent bonds, are used to lecular chemistry from the three-dimensional (3D) realm assemble by design large structures from tailored mol- to the two-dimensional (2D). The discovery and application ecules.1,2 Since the pioneering work of Lehn, Cram, and of the scanning tunneling microscope has made this Pedersen,3 there has been a steadily increasing interest evolution to 2D supramolecular studies possible. The in the development and application of supramolecular design strategies discovered for 3D supramolecular chem- chemistry. In its beginning, focus was on molecular istry can be applied to the adsorbed state. Moreover, there recognition, which is the selective binding of a guest by is a particular relevance of the surface state to supramo- a host using non-covalent interactions.4 As the field grew, lecular synthesis with physisorbed molecules, because the rational design of molecular crystals using supramo- many of the weaker interactions used in generating lecular interactions became an area of interest.5-7 Hy- synthons are probably distorted or destroyed in fluid drogen bonding is the most common supramolecular solution and in chemisorption. The weak lateral forces interaction; however, other interactions including halogen- exerted by the surface upon physisorbed molecules, and halogen,8 halogen-nitrogen,9,10 halogen-oxygen,7 elec- the image charges that occur in metal substrates, allow trostatic interactions, 11-15 and weak electron donor- these weaker intermolecular forces to play a significant acceptor complexation16 have been used to organize role in the formation of long-range order in the adsorbed molecules within a crystal. phase. While some of the supramolecular synthons developed for crystal synthesis may be inappropriate for * To whom correspondence should be addressed. generating surface structures because of the planar E-mail: [email protected]. template effect of the substrate, others may have their (1) Lehn, J. M. Supramolecular Chemistry: Concept and Perspectives; stability enhanced by the reduction in entropy, the steric VCH: Weinheim, Germany, 1995. constraints imposed by the surface, and the electrostatic (2) Lehn, J. M. Proc. Natl. Acad. Sci. U.S.A. 2002, 99, 4763. (3) 1987 Noble Prize in Chemistry. (4) Gale, P. A. Philos. Trans. R. Soc. London, Ser. A 2000, 358, 431. (16) Bosch, E.; Radford, R.; Barnes, C. Org. Lett. 2001, 3, 881. (5) Reddy, D. S.; Craig, D. C.; Desiraju, G. M. J. Am. Chem. Soc. (17) De Feyter, S.; De Schryver, F. C. Chem. Soc. Rev. 2003, 32, 139. 1996, 118, 8, 4090. (18) Yablon, D. G.; Giancarlo, L. C.; Flynn, G. W. J. Phys. Chem. B (6) Gillard, R.; Stoddard, J.; White, A.; Williams, B.; Williams, D. J. 2000, 104, 7627. Org. Chem. 1996, 61, 4504. (19) Yablon, D.; Guo, J.; Knapp, D.; Fang, H.; Flynn, G. W. J. Phys. (7) Desiraju, G. R. Angew. Chem., Int. Ed. Engl. 1995, 34, 2311. Chem. B 2001, 105, 4313. (8) Scmhidt, G. M. Pure Appl. Chem. 1971, 27, 647. (20) Cai, Y.; Bernasek, S. L. J. Am. Chem. Soc. 2003, 125, 1655. (9) Reddy, D. S.; Ovchinnikov, Y.; Shishkin, Y.; Struchkov, Y.; (21) Yoshimoto, S.; Suto, K.; Itaya, K.; Kobayashi, N. Chem. Commun. Desiraju, G. J. Am. Chem. Soc. 1996, 118, 4085, and references therein. 2003, 2174. (10) Xu, K.; Ho, D.; Pascal, R. J. Org. Chem. 1995, 60, 7186. (22) Whitesides, G. M.; Boncheva, M. Proc. Natl. Aacad. Sci. U.S.A. (11) Coates, G.; Dunn, A.; Henling, A.; Dougherty, D.; Grubbs, R. H. 2002, 99, 4769. Angew. Chem., Int. Ed. Engl. 1997, 36, 248. (23) Griessl, S. J. H.; Lackinger, M.; Jamitzky, F.; Markert, T.; (12) Coates, G.; Dunn, A.; Henling, L.; Ziller, J.; Lobkovsky, E.; Hietschol, M.; Heckl, W. M. J. Phys. Chem. B 2004, 108, 11556. Grubbs, R. H. J. Am. Chem. Soc. 1998, 120, 3641. (24) Hipps, K. W.; Scudiero, L.; Barlow, D. E.; Cooke, M. P. J. Am. (13) Gillard, R.; Stoddard, J.; White, A.; Williams, B.; Williams, D. Chem. Soc. 2002, 124, 2126. J. Org. Chem. 1996, 61, 4504. (25) Scudiero, L.; Hipps, K. W.; Barlow, D. E. J. Phys. Chem. B 2003, (14) Williams, J. H. Acc. Chem. Res. 1993, 26, 593. 107, 2903. (15) Hunter, C.; Lu, X.; Kapteijn, G.; Koten, G. J. Chem. Soc., Faraday (26) Lei, S.; Wang, C.; Wan, L.; Bai, C. J. Phys. Chem. B 2004, 108, Trans. 1995, 91, 2009. 1173. 10.1021/la047726j CCC: $30.25 © 2005 American Chemical Society Published on Web 12/30/2004 920 Langmuir, Vol. 21, No. 3, 2005 Gyarfas et al. environment provided in the case of a metallic substrate. We restrict our consideration to physisorbed molecules to ensure that the lateral intermolecular interactions can play a significant role in coadsorbate ordering. Scanning tunneling microscopy (STM) is the only technique that can provide detailed sub-nanometer struc- tural analysis at the solid-solution interface in real time. Through its application, a view is provided of the elegant architectures that occur in what one might think was the relativelydisorderedinterfacebetweensolidandsolution.17-21,23,26 STM has also been key to characterizing 2D supramo- lecular structures resulting from vapor deposition on solid surfaces.24,25,27,28 In the present study we will use STM to Figure 1. Constant-current STM images of two different probe the interfacial layer that results when Au(111) comes samples of coronene in octanoic acid on Au(111). (A) Bias voltage, into contact with a solution of coronene in various alkane -0.40 V; set point, 500 pA; coronene spacing, 1.47 nm. (B) Bias acids. Our interest in this system was generated by the voltage, -0.70 V; set point, 300 pA; coronene spacing, 1.24 nm. rich spectrum of potential weak interactions. The alkane The gray scale extends over 0.12 nm. acid might interact with the gold through dipole-induced dipole interactions, leading to a standing configuration, The STM head used was produced by Digital Instruments or dispersion type interactions might produce a surface (now Veeco Metrology). A Digital Instruments Nanoscope E covered by alkane acids in the striped array (lamellae) controller was used to acquire the reported data. STM image analysis was performed with the SPIP38 commercial software normally seen on graphite. Coronene is known to physisorb package. Constant-current images are reported, and any filtering on graphite from the vapor in a close-packed hexagonal is indicated in the appropriate figure caption. Both etched and structure with the coronene lying flat on the surface and cut Pt0.8Ir0.2 tips were used. In-plane spacing measured by STM having a lattice spacing of about 1.1 nm.29 STM studies was calibrated using the graphite lattice. In-plane measurements of coronene adsorbed Au and Ag reported a coronene have a precision of less than (0.04 nm and an average absolute spacing of about 1.2 nm.30-32 Another possibility is that error of <0.04 nm. All measurements were made at 21 ( 2 °C. coronene may adsorb onto lamellae of alkane acids (similar Results to phthalocyanine and tridedycelamine (TDA) on graph- 33 STM images from these systems varied widely in ite ). Finally, the potential for hydrogen bonding between quality. Good clear images would be replaced by unstruc- coronene and the carboxyl must be considered. What we tured noise for no apparent reason. At other times, changes actually find is a competition between several of these in bias voltage would lead to significant changes in the factors. observed image. We attribute these changes as principally due to the fact that the system is in dynamic equilibrium Experimental Section between the adsorbed layer and solution. The intrinsic Hexanoic acid (C O H ), heptanoic acid (C O H ), and exchange processes between solution and adsorbed phase 6 2 12 7 2 14 molecules, the structural changes induced by the STM tip octanoic acid (C8O2H16), all g99%, were used as supplied by Sigma-Aldrich. Coronene was also provided by Aldrich and was during scanning, and the bias voltage as it brings the labeled as sublimed and 99% purity.
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