Abstract
We present an interplay of high-resolution scanning tunneling microscopy imaging and the corresponding theoretical calculations based on elastic scattering quantum chemistry techniques of the adsorption of a gold-functionalized rosette assembly and its building blocks on a Au(111) surface with the goal of exploring how to fabricate functional 3-D molecular nanostructures on surfaces. The supramolecular rosette assembly stabilized by multiple hydrogen bonds has been sublimed onto the Au(111) surface under ultra-high vacuum conditions; the resulting surface nanostructures are distinctly different from those formed by the individual molecular building blocks of the rosette assembly, suggesting that the assembly itself can be transferred intact to the surface by in situ thermal sublimation. This unanticipated result will open up new perspectives for growth of complex 3-D supramolecular nanostructures at the vacuum-solid interface.
References
Barth, J. V.; Weckesser, J.; Trimarchi, G.; Vladimirova, M.; De Vita, A.; Cai, C. Z.; Brune, H.; Gunter, P.; Kern, K. Stereochemical effects in supramolecular self-assembly at surfaces: 1-D versus 2-D enantiomorphic ordering for PVBA and PEBA on Ag(111). J. Am. Chem. Soc. 2002, 124, 7991–8000.
Xu, W.; Kelly, R. E. A.; Otero, R.; Schöck, M.; Lægsgaard, E.; Stensgaard, I.; Kantorovich, L. N.; Besenbacher, F. Probing the hierarchy of thymine-thymine interactions in self-assembled structures by manipulation with scanning tunneling microscopy. Small 2007, 3, 2011–2014.
Otero, R.; Lukas, M.; Kelly, R. E. A.; Xu, W.; Lægsgaard, E.; Stensgaard, I.; Kantorovich, L. N.; Besenbacher, F. Elementary structural motifs in a random network of cytosine adsorbed on a gold(111) surface. Science 2008, 319, 312–315.
Chen, Q.; Richardson, N. Enantiomeric interactions between nucleic acid bases and amino acids on solid surfaces. Nat. Mater. 2003, 2, 324–328.
Theobald, J. A.; Oxtoby, N. S.; Phillips, M. A.; Champness, N. R.; Beton, P. H. Controlling molecular deposition and layer structure with supramolecular surface assemblies. Nature 2003, 424, 1029–1031.
Kong, X. H.; Deng, K.; Yang, Y. L.; Zeng, Q. D.; Wang, C. H-bond switching mediated multiple flexibility in supramolecular host-guest architectures. J. Phys. Chem. C 2007, 111, 17382–17387.
Nath, K. G.; Ivasenko, O.; Miwa, J. A.; Dang, H.; Wuest, J. D.; Nanci, A.; Perepichka, D. F.; Rosei, F. Rational modulation of the periodicity in linear hydrogen-bonded assemblies of trimesic acid on surfaces. J. Am. Chem. Soc. 2006, 128, 4212–4213.
Wintjes, N.; Bonifazi, D.; Cheng, F.; Kiebele, A.; Stöhr, M.; Jung, T.; Spillmann, H.; Diederich, F. A supramolecular multiposition rotary device. Angew. Chem. Int. Ed. 2007, 46, 4089–4092.
Schiffrin, A.; Riemann, A.; Auwärter, W.; Pennec, Y.; Weber-Bargioni, A.; Cvetko, D.; Cossaro, A.; Morgante, A.; Barth, J. V. Zwitterionic self-assembly of L-methionine nanogratings on the Ag(111) surface. Proc. Natl. Acad. Sci. USA 2007, 104, 5279–5284.
Spillmann, H.; Kiebele, A.; Stohr, M.; Jung, T. A.; Bonifazi, D.; Cheng, F. Y.; Diederich, F. A two-dimensional porphyrin-based porous network featuring communicating cavities for the templated complexation of fullerenes. Adv. Mater. 2006, 18, 275–279.
Kelly, R. E. A.; Xu, W.; Lukas, M.; Otero, R.; Mura, M.; Lee, Y.; Lægsgaard, E.; Stensgaard, I.; Kantorovich, L. N.; Besenbacher, F. An investigation into the interactions between self-assembled adenine molecules and a Au(111) surface. Small 2008, 4, 1494–1500.
Schnadt, J.; Rauls, E.; Xu, W.; Vang, R. T.; Knudsen, J.; Laegsgaard, E.; Li, Z.; Hammer, B.; Besenbacher, F. Extended one-dimensional supramolecular assembly on a stepped surface. Phys. Rev. Lett. 2008, 100, 046103.
Barth, J. V.; Costantini, G.; Kern, K. Engineering atomic and molecular nanostructures at surfaces. Nature 2005, 437, 671–679.
De Feyter, S.; De Schryver, F. C. Two-dimensional supramolecular self-assembly probed by scanning tunneling microscopy. Chem. Soc. Rev. 2003, 32, 139–150.
Wan, L. J. Fabricating and controlling molecular self-organization at solid surfaces: Studies by scanning tunneling microscopy. Acc. Chem. Res. 2006, 39, 334–342.
Otero, R.; Rosei, F.; Besenbacher, F. Scanning tunneling microscopy manipulation of complex organic molecules on solid surfaces. Annu. Rev. Phys. Chem. 2006, 57, 497–525.
Prins, L. J.; De Jong, F.; Timmerman, P.; Reinhoudt, D. N. An enantiomerically pure hydrogen-bonded assembly. Nature 2000, 408, 181–184.
Vázquez-Campos, S.; Péter, M.; Dong, M.; Xu, S.; Xu, W.; Gersen, H.; Linderoth, T. R.; Schönherr, H.; Besenbacher, F.; Crego-Calama, M.; Reinhoudt, D. N. Self-organization of gold-containing hydrogen-bonded rosette assemblies on graphite surface. Langmuir 2007, 23, 10294–10298.
Xu, W.; Dong, M.; Gersen, H.; Rauls, E.; Vázquez-Campos, S.; Crego-Calama, M.; Reinhoudt, D. N.; Stensgaard, I.; Lægsgaard, E.; Linderoth, T. R.; Besenbacher, F. Cyanuric acid and melamine on Au(111): Structure and energetics of hydrogen-bonded networks. Small 2007, 3, 854–858.
Xu, W.; Dong, M.; Vázquez-Campos, S.; Gersen, H.; Lægsgaard, E.; Stensgaard, I.; Crego-Calama, M.; Reinhoudt, D. N.; Linderoth, T. R.; Besenbacher, F. Enhanced stability of large molecules vacuum-sublimated onto Au(111) achieved by incorporation of coordinated Au-atoms. J. Am. Chem. Soc. 2007, 129, 10624–10625.
Xu, W.; Dong, M.; Gersen, H.; Rauls, E.; Vázquez-Campos, S.; Crego-Calama, M.; Reinhoudt, D. N.; Lægsgaard, E.; Stensgaard, I.; Linderoth, T. R.; Besenbacher, F. Influence of alkyl side chains on hydrogen-bonded molecular surface nanostructures. Small 2008, 4, 1620–1623.
Mullen, T. J.; Dameron, A. A.; Weiss, P. S. Directed assembly and separation of self-assembled monolayers via electrochemical processing. J. Phys. Chem. B 2006, 110, 14410–14417.
Monnell, J. D.; Stapleton, J. J.; Dirk, S. M.; Reinerth, W. A.; Tour, J. M.; Allara, D. L.; Weiss, P. S. Relative conductances of alkaneselenolate and alkanethiolate monolayers on Au{111}. J. Phys. Chem. B 2005, 109, 20343–20349.
Kumar, A. S.; Ye, T.; Takami, T.; Yu, B. -C.; Flatt, A. K.; Tour, J. M.; Weiss, P. S. Reversible photo-switching of single azobenzene molecules in controlled nanoscale environments. Nano Lett. 2008, 8, 1644–1648.
Bouju, X.; Joachim, C.; Girard, C.; Tang, H. Mechanics of (Xe)N atomic chains under STM manipulation. Phys. Rev. B 2001, 63, 085415.
Ample, F.; Joachim, C. A semi-empirical study of polyacene molecules adsorbed on a Cu(110) surface. Surf. Sci. 2006, 600, 3243–3251.
Sautet, P.; Joachim, C. Electronic transmission coefficient for the single-impurity problem in the scattering-matrix approach. Phys Rev. B 1988, 38, 12238–12247.
Pizzagali, L.; Joachim, C.; Bouju, X.; Girard, C. The resistance of a (Xe)n atomic wire. Europhys. Lett. 1997, 38, 97–102.
Seto, C. T.; Whitesides, G. M. Synthesis, characterization, and thermodynamic analysis of a 1 + 1 self-assembling structure based on the cyanuric acid·cntdot·melamine lattice. J. Am. Chem. Soc. 1993, 115, 1330–1340.
Prins, L. J.; Neuteboom, E. E.; Paraschiv, V.; Crego-Calama, M.; Timmerman, P.; Reinhoudt, D. N. Kinetic stabilities of double, tetra-, and hexarosette hydrogenbonded assemblies. J. Org. Chem. 2002, 67, 4808–4820.
Staniec, P. A.; Perdigão, L. M. A.; Rogers, B. L.; Champness, N. R.; Beton P. H. Honeycomb networks and chiral superstructures formed by cyanuric acid and melamine on Au(111). J. Phys. Chem. C 2007, 111, 886–893.
van Manen, H. J.; Paraschiv, V.; Garcia-Lopez, J. J.; Schonherr, H.; Zapotoczny, S.; Vancso, G. J.; Crego-Calama, M.; Reinhoudt, D. N. Hydrogen-bonded assemblies as a scaffold for metal-containing nanostructures: From zero to two dimensions. Nano Lett. 2004, 4, 441–446.
Lægsgaard, E.; Osterlund, L.; Thostrup, P.; Rasmussen, P. B.; Stensgaard, I.; Besenbacher, F. A high-pressure scanning tunneling microscope. Rev. Sci. Instrum. 2001, 72, 3537–3542.
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Xu, W., Dong, M., Gersen, H. et al. Exploring the transferability of large supramolecular assemblies to the vacuum-solid interface. Nano Res. 2, 535–542 (2009). https://doi.org/10.1007/s12274-009-9051-6
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DOI: https://doi.org/10.1007/s12274-009-9051-6
Keywords
- Self-assembly
- surface nanostructures
- scanning tunneling microscopy
- supramolecular assembly
- hydrogen bonding