Abstract
The adsorption and self-assembly of benzoic acid (BA), isophthalic acid (IA), and trimesic acid (TMA) on Au(111) single crystals and on Au(111-25 nm) quasi-single crystalline film electrodes have been investigated in 0.1 M HClO4 by combining in situ surface-enhanced infrared reflection absorption spectroscopy (SEIRAS) and scanning tunneling microscopy (STM) with cyclic voltammetry. All three acids are physisorbed on the electrode surface in a planar orientation at negative charge densities. Excursion to positive charge densities (or more positive potentials) causes an orientation change from planar to perpendicular. Chemisorbed structures are formed through the coordination of a deprotonated carboxyl group to the positively charged electrode surface. The three acid molecules assemble in different ordered patterns, which are controlled by π-stacking (BA) or intermolecular hydrogen bonds between COOH groups (IA, TMA). A detailed analysis of the potential and time dependencies of the ν(C=O), νs(OCO), and ν(C–OH) vibration modes shows that the strength of lateral interactions increases upon chemisorption with an increasing number of COOH groups in the sequence of BA<IA<TMA. The vibration bands shift to higher wavenumbers due to dipole–dipole coupling, Stark tuning, and electron back donation from the electrode to COO−. In addition, an “indirect” electron donation to the COOH groups takes place via the conjugated molecular skeleton superimposed on the intermolecular hydrogen bonding.
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References
Bailey M, Brown CJ (1967) Acta Crystallogr B 22:387
Alcala R, Martinez-Carrera S (1972) Acta Crystallogr B 25:1671
De Feyter S, Gesquiere A, Abdel-Mottaleb MM, Grim PCM, De Shryver FC, Meiners C, Sieffert M, Valiyaveettil S, Müllen K (2000) Acc Chem Res 33:520
Melendres R, Hamilton AD (1998) Top Curr Chem 197:97
Barth JV, Costantini G, Kern K (2005) Nature 437:671
Herbstein FH (1996) In: Atwood JL, MacNico DD, Vögtle DD, Lehn JM (eds) Comprehenive supramolecular chemistry, vol 6. Pergamon, New York, pp 61
Kolotuchin SV, Thiessen PA, Fenlon EE, Wilson SR, Loweth CJ, Zimmerman SC (1999) Chem Eur J 5(9):2537
Chatterjee S, Pedireddi VR, Ranganathan A, Rao CNR (2000) J Mol Structure 520:107
Barth JV, Wechesser J, Lin N, Dmitriev A, Kern K (2003) Appl Phys A 76:645
Ermer O, Neudörfl J (2001) Chem Eur J 7:4961
Dai JC, Hu SM, Wu XT, Fu ZY, Du WX, Zhang HH, Sun RQ (2003) New J Chem 27:94
Melendez RE, Shrama CVK, Zaworotko MJ, Bauer C, Rogers RD (1996) Angew Chem Int Ed Engl 35:2213
Lin N, Dmitriev A, Weckesser J, Barth JV, Kern K (2002) Angew Chem Int Ed Engl 41:4779
Messina P, Dmitriev A, Lin N, Spillmann H, Abel M, Barth JV, Kern K (2002) J Am Chem Soc 124:14000
Ishikawa Y, Ohira A, Sakata M, Hirayama C, Kunitake MJ (2002) Chem Soc Chem Commun 2652
Su GJ, Zhang HM, Wan LJ, Bai CL, Wandlowski T (2004) J Phys Chem B 108:1931
Ikezawa Y, Sekiguchi R, Kitazume T (2000) Electrochim Acta 46:731
Li HQ, Roscoe SG, Lipkowski J (1999) J Electroanal Chem 478:67
Ikezawa Y, Yoshida A, Sekiguchi R (2000) Electrochim Acta 46:769
Lee MW, Kim MS, Kim K (1997) J Mol Struct 415:93
Dretschkow T, Wandlowski T (2003) Top Appl Phys 85:259
Schultz ZD, Gewirth AA (2005) Anal Chem 77:7373
Wandlowski T, Ataka K, Pronkin S, Diesing D (2004) Electrochim Acta 49:1233
Pronkin S, Wandlowski T (2003) J Electroanal Chem 550–551:131
Li HQ, Roscoe SG, Lipkowski J (2000) J Solution Chem 29:987
Osawa M, Ikeda M (1991) J Phys Chem 95:9914
Han B, Li Z, Pronkin S, Wandlowski T (2004) Can J Chem 82(10):1481
Li Z, Han B, Wandlowski T (2005) Langmuir 21:6915
Li Z, Han B, Wandlowski T (2007) (in preparation)
de Feyter S, Gesquiere A, Klapper M, Müllen K, Schryver FC (2003) Nano Lett 3:1485
Arenas JF, Marcos JI (1979) Spectrochim Acta 35A:355
Gonzalez-Sanchez F (1957) Spectrochim Acta 12:17
Lide DR (ed) (2001) In: Handbook of chemistry and physics, 82nd edn. CRC Press, Boca Raton, pp 8–45
Dean JA (1985) In: Lange’s handbook of chemistry, 13th edn. McGraw-Hill, pp 5–42
Osawa M (1997) Bull Chem Soc Jpn 70:2861
Osawa M (2002) In: Chalmers JM, Griffiths PR (eds) Handbook of vibrational spectroscopy, vol 1. Theory and instrumentation. Wiley, Chichister, p 785
Nichols R (1992) In: Lipkowski J, Ross PN (eds) Adsorption of molecules at electrodes. VCH, New York, p 347
Lambert DK (1996) Electrochim Acta 41:623
Ashley K, Pons S (1988) Chem Rev 88:673
Ataka K, Osawa M (1999) J Electroanal Chem 460:188
Wandlowski T, Ataka K, Mayer D (2002) Langmuir 18:4331
Noda H, Wan LJ, Osawa M (2001) Phys Chem Chem Phys 3:3336
Kwon YJ, Son DH, Ahn SJ, Kim MS, Kim K (1994) J Phys Chem 98:8481
Kim SH, Ahn SJ, Kim K (1996) J Phys Chem 100:7174
Colthup NB, Daley LH, Wiberly SE (1990) Introduction to infrared and Raman spectroscopy. Academic Press, Boston
Acknowledgements
The work was supported by the Volkswagen foundation under grant No. I80–879, IFMIT and the Research Center Jülich. The authors acknowledge the skilful help of U. Linke and of H. J. Bierfeld in preparing the gold single crystals and gold film electrodes.
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Han, B., Li, Z. & Wandlowski, T. Adsorption and self-assembly of aromatic carboxylic acids on Au/electrolyte interfaces. Anal Bioanal Chem 388, 121–129 (2007). https://doi.org/10.1007/s00216-007-1166-6
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DOI: https://doi.org/10.1007/s00216-007-1166-6