AFM Height Measurements of Molecular Layers of a Carbocyanine Dye


Atomic force microscopy (AFM) was used for the morphological characterization and precise height meas-urements of two-dimensional molecular layers of carbocyanine dye 3,3’-di(r-sulfopropyl)-4,4’,5,5’-dibenzo-9-ethylthiacarbocyanine betaine pyridinium salt. The AFM measurements reveal three morphological types of molecular aggregates: leaves, stripes and spots. The leaves are stripes have same monolayer height ~1.4 nm and different crystal shapes: the leaves are monoloyers with the lens shape and the stripes are bilay-ers with the shape of extended rectangles. The monolayer height ~1.4 nm was interpreted as indicating the symmetrical packing arrangement of dye molecules. In the symmetrical monolayer, the sulfopropyl groups of all-trans monomer units are located on both monolayer sides whereas the adjacent stacked dye molecules have a lateral slippage providing the J-aggregate optical properties. The lower height of spots ~1 nm was explained by the model of an asymmetric monolayer with sulfopropyl groups of all-trans monomers occupy-ing the same position with respect to the monolayer plane. The packing arrangement of all-trans monomers in the asymmetric monolayer corresponds to H-aggregate. The alternative models of the packing arrange-ment in monolayers with mono-cis1 monomer configuration are discussed.

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V. Prokhorov, S. Pozin, D. Lypenko, O. Perelygina, E. Mal’tsev and A. Vannikov, "AFM Height Measurements of Molecular Layers of a Carbocyanine Dye," World Journal of Nano Science and Engineering, Vol. 1 No. 3, 2011, pp. 67-72. doi: 10.4236/wjnse.2011.13010.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] F. C. Spano, “The Spectral Signatures of Frenkel Polarons in H- and J-Aggregates,” Accounts of Chemical Research, Vol. 43, No. 3, 2010, pp. 429-439. doi:10.1021/ar900233v
[2] V. Czikkely, H. D. F?rsterling and H. Kuhn, “Extended Dipole Model for Aggregates of Dye Molecules,” Chemical Physics Letters, Vol. 6, No. 3, 1970, pp. 207-210. doi:10.1016/0009-2614(70)80220-2
[3] H. Yao, “Morphology Transformations in Solutions: Dynamic Supramolecular Aggregates,” Annual Repports on the Progress of Chemistry, Section C, Vol. 100, 2004, pp. 99-148. doi:10.1039/b313661m
[4] R. H. von Berlepsch, C. B?ttcher, A. Ouart, C. Burger, S. D?hne and S. Kirstein, “Supramolecular Structures of J- Aggregates of Carbocyanine Dyes in Solution,” The Journal of Physical Chemistry B, Vol. 104, No. 22, 2000, pp. 5255-5262. doi:10.1021/jp000220z
[5] H. von Berlepsch, S. Kirstein and C. B?ttcher, “Supra- molecular Structure of J-Aggregates of a Sulfonate Substi-tuted Amphiphilic Carbocyanine Dye in Solution: Metha-nol-Induced Ribbon-to-Tubule Transformation,” The Journal of Physical Chemistry B, Vol. 108, No. 48, 2004, pp. 18725-18733. doi:10.1021/jp046546f
[6] H. Yao, K. Domoto, T. Isohashi and K. Kimura, “In Situ Detection of Birefringent Mesoscopic H- and J-Aggregates of Thiacarbocyanine Dye in Solution,” Langmuir, Vol. 21, No. 3, 2005, pp. 1067-1073. doi:10.1021/la0479004
[7] H. Yao, T. Isohashi and K. Kimura, “Electrolyte-Induced Mesoscopic Aggregation of Thiacarbocyanine Dye in Aqueous Solution: Counterion Size Specificity,” The Journal of Physical Chemistry B, Vol. 111, No. 25, 2007, pp. 7176-7183. doi:10.1021/jp070520h
[8] E. I. Mal’tsev, D. A. Lypenko, B. I. Shapiro, M. A. Brusentseva, G. H. W. Milburn, J. Wright, A. Hendriksen, V. I. Berendyaev, B. V. Kotov and A. V. Vannikov, “Electroluminescence of Polymer/J-Aggregate Composites,” Applied Physics Letters, Vol. 75, No. 13, 1999, pp. 1896-1898.
[9] E. I. Mal’tsev, D. A. Lypenko, V. V. Bobinkin, A. R. Tameev, B. I. Shapiro, H. F. M. Schoo and A. V. Vannikov, “Near-Infrared Electroluminescence in Polymer Composites Based on Organic Nanocrystals,” Applied Physics Letters, Vol. 81, No. 16, 2002, pp. 3088-3090.
[10] V. V. Prokhorov, E. I. Mal’tsev, O. M. Perelygina, D. A. Lypenko, S. I. Pozin and A. V. Vannikov, “High Precision Nanoscale AFM Height Measurements of J-Aggregates,” Nanotechnology in Russia, Vol. 6, No. 5-6, 2011, pp. 286-297. doi:10.1134/S199507801103013X
[11] R. Garcia and R. Pérez, “Dynamic Atomic Force Microscopy Methods,” Surface Science Reports, Vol. 47, No. 6-8, 2002, pp. 197-301. doi:10.1016/S0167-5729(02)00077-8
[12] G. Zhang and M. Liu, “Interfacial Assemblies of Cyanine Dyes and Gemini Amphiphiles with Rigid Spacers: Regulation and Interconversion of the Aggregates,” The Journal of Physical Chemistry B, Vol. 112, No. 25, 2008, pp. 7430-7437. doi:10.1021/jp8005298
[13] M. V. Alfimov, A. A. Shtykova and V. F. Razumov, “Photo- and Thermoinitiated Formation of J- and H-Aggregates in Amorphous Dispersion of a Carbocyanine Dye,” High Energy Chemistry, Vol. 40, No. 1, 2006, pp. 18-21.
[14] T. D. Slavnova, A. K. Chibisov and H. G?rner, “Kinetics of Salt-Induced J-Aggregation of Cyanine Dyes,” The Journal of Physical Chemistry A, Vol. 109, No. 21, 2005, pp. 4758-4765. doi:10.1021/jp058014k
[15] L. D. Bakalis, I. Rubtsov and J. Knoester, “Absorption Spectra of Mixed Two-Dimensional Cyanine Aggregates on Silver Halide Substrates,” The Journal of Chemical Physics, Vol. 117, No. 11, 2002, pp. 5393-5403. doi:10.1063/1.1499958
[16] G. Busse, B. Frederichs, N. Kh. Petrov and S. Techert, “Structure Determination of Thiacyanine Dye J-Aggregates in Thin Films: Comparison between Spectroscopy and Wide Angle X-Ray Scattering,” Physical Chemistry Chemical Physics, Vol. 6, 2004, pp. 3309-3314. doi:10.1039/b400212a
[17] G. N. Chuev and M. V. Fedorov, “Reference Interaction Site Model Study of Self-Aggregating Cyanine Dyes,” The Journal of Chemical Physics, Vol. 131, No. 7, 2009, Article ID: 074503.

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