Abstract
Molecular-resolution scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) are powerful tools for probing the electrical properties of individual π-electron systems, providing us with vital information on adsorption geometry, intermolecular patterns, and local conductivity of single molecules. These characteristics allow us to understand the function of single molecules and the mechanism of how they operate which in turn allow us to intelligently design more complicated multicomponent architectures. In this chapter, characterizations of π-electron systems by STM and STS are demonstrated. Experimental conditions of STM and STS for the measurements of π-electron systems are summarized. Molecular-resolution STM images of endohedral metallofullerenes and subporphyrins are shown. STS measurements reveal electrical properties on π-electron systems such as HOMO and LUMO. Molecular resonant tunneling behaviors of tribenzosubporphyrin are presented.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Kano S, Tada T, Majima Y (2015) Nanoparticle characterization based on STM and STS. Chem Soc Rev 44:970
Iwamoto M, Ogawa D, Yasutake Y, Azuma Y, Umemoto H, Ohashi K, Izumi N, Shinohara H, Majima Y (2010) Molecular orientation of individual Lu@C82 molecules demonstrated by scanning tunneling microscopy. J Phys Chem C 114:14704
Yasutake Y, Shi Z, Okazaki T, Shinohara H, Majima Y (2005) Single molecular orientation switching of an endohedral metallofullerene. Nano Lett 5:1057–1060
Majima Y, Ogawa D, Iwamoto M, Azuma Y, Tsurumaki E, Osuka A (2013) Negative differential resistance by molecular resonant tunneling between neutral tribenzosubporphine anchored to a Au(111) surface and tribenzosubporphine cation adsorbed on to a Tungsten tip. J Am Chem Soc 135:14159–14166
Inokuma Y, Kwon JH, Ahn TK, Yoon M-C, Kim D, Osuka A (2006) Tribenzosubporphines: synthesis and characterization. Angew Chem Int Ed 45:961
Inokuma Y, Osuka A (2008) Subporphyrins: emerging contracted porphyrins with aromatic 14 pi-electronic systems and bowl-shaped structures: rational and unexpected synthetic routes. Dalton Trans 19:2517
Osuka A, Tsurumaki E, Tanaka T (2011) Subporphyrins: a legitimate ring-contracted porphyrin with versatile electronic and optical properties. Bull Chem Soc Jpn 84:679
Kohn W, Sham L (1965) Quantum density oscillations in an inhomogeneous electron gas. Phys Rev 140:A1133
Parr RG, Yang W (1994) Density-functional theory of atoms and molecules. Oxford Science, Oxford
Becke AD (1993) Density – functional thermochemistry. III. The role of exact exchange. J Chem Phys 98:5648
Lee C, Yang W, Parr RG (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B 37:785
Gaussian 09, Revision D. 01 Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA, Peralta JE Jr, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009). Gaussian, Inc., Wallingford CT
Zhao J, Zeng C, Cheng X, Wang K, Wang G, Yang J, Hou JG, Zhu Q (2005) Single C59N molecule as a molecular rectifier. Phys Rev Lett 95:045502
Oyama Y, Majima Y, Iwamoto M (1999) Tunneling resistance of double-barrier tunneling structures with an alkanethiol-protected Au nanoparticle. J Appl Phys 86:7087
Zhang H, Yasutake Y, Shichibu Y, Teranishi T, Majima Y (2005) Phys Rev B 72:205441
Porter MD, Bright TB, Allara DL, Chidsey CED (1987) Spontaneously organized molecular assemblies. 4. Structural characterization of n-alkyl thiol monolayers on gold by optical ellipsometry, infrared spectroscopy, and electrochemistry. J Am Chem Soc 109:3559
Bumm LA, Arnold JJ, Dunbar TD, Allara DL, Weiss PS (1999) Electron transfer through organic molecules. J Phys Chem B 103:8122
Acknowledgements
The author thanks Prof. A. Osaka for synthesis of tribenzosubporphines and fruitful discussions. The work was partially supported by a Grant-in-Aid for Scientific Research on Innovative Areas (No. 20108011, π – Space) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), and MEXT Elements Strategy Initiative to Form Core Research Center, and the BK Plus program, Basic Science Research program (NRF-2014R1A1030419).
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2015 Springer Japan
About this chapter
Cite this chapter
Majima, Y. (2015). STM Characterization of π-Electron Systems. In: Akasaka, T., Osuka, A., Fukuzumi, S., Kandori, H., Aso, Y. (eds) Chemical Science of π-Electron Systems. Springer, Tokyo. https://doi.org/10.1007/978-4-431-55357-1_37
Download citation
DOI: https://doi.org/10.1007/978-4-431-55357-1_37
Publisher Name: Springer, Tokyo
Print ISBN: 978-4-431-55356-4
Online ISBN: 978-4-431-55357-1
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)