Supramolecular chirality at the air/water interface [Invited]

Second Harmonic Generation (SHG) was used to study the non-linear optical properties of a two-dimensional film formed by the achiral amphiphilic compound 5-(octadecyloxy)-2-(2-thiazolylazo) phenol (TARC18) at the air-water interface. The S-polarized SHG intensity was measured as a function of the incident fundamental wave polarization angle during the monolayer compression. The method was applied to follow the emergence of chirality during the film compression and at constant surface pressure. The formation of molecular aggregates revealing supramolecular chirality was then demonstrated. It was shown furthermore that the origin of chirality was dominated by the magnetic contributions.

[1]  K. Eisenthal,et al.  Liquid Interfaces Probed by Second-Harmonic and Sum-Frequency Spectroscopy. , 1996, Chemical reviews.

[2]  R. Raval.  Chiral expression from molecular assemblies at metal surfaces: insights from surface science techniques. , 2009, Chemical Society reviews.

[3]  G. Flynn,et al.  Raising flags: applications of chemical marker groups to study self-assembly, chirality, and orientation of interfacial films by scanning tunneling microscopy. , 2000, Accounts of chemical research.

[4]  Pierre F. Brevet.  Phenomenological three-layer model for surface second-harmonic generation at the interface between two centrosymmetric media , 1996 .

[5]  John E. Sipe,et al.  Phenomenological treatment of surface second-harmonic generation , 1988 .

[6]  Christian Jonin,et al.  Chirality in molecular films at the air-water interface , 2011, OPTO.

[7]  Thierry Boulesteix,et al.  Chiroptical effects in the second harmonic signal of collagens I and IV. , 2005, Journal of the American Chemical Society.

[8]  Y. Rao,et al.  Inhomogeneous and Spontaneous Formation of Chirality in the Langmuir Monolayer of Achiral Molecules at the Air/Water Interface Probed by In Situ Surface Second Harmonic Generation Linear Dichroism , 2009 .

[9]  J. Zasadzinski,et al.  Spontaneous chiral symmetry breaking by achiral molecules in a Langmuir–Blodgett film , 1994, Nature.

[10]  S. De Feyter,et al.  Two-dimensional chirality at liquid-solid interfaces. , 2009, Chemical Society reviews.

[11]  François Hache,et al.  Off resonance second order optical activity of isotropic layers of chiral molecules: Observation of electric and magnetic contributions , 1998 .

[12]  A. Persoons,et al.  Linearly and Circularly Polarized Probes of Second-Order Optical Activity of Chiral Surfaces , 1996, Organic Thin Films for Photonic Applications.

[13]  Pierre-François Brevet,et al.  Second Harmonic Generation, a new approach for analyzing the interfacial properties of a short tryptophan-rich peptide , 2010 .

[14]  F. D. De Schryver,et al.  Losing the expression of molecular chirality in self-assembled physisorbed monolayers. , 2005, Nano letters.

[15]  H. Nakahara,et al.  Complex Formation between Monolayers of a Novel Amphiphilic Thiazolylazo Dye and Transition Metal Ions at the Air/Water Interface , 1997 .

[16]  Jeffery J. Maki,et al.  Second‐harmonic generation from chiral surfaces , 1994 .

[17]  Isabelle Russier-Antoine,et al.  Compression Induced Chirality in Dense Molecular Films at the Air−Water Interface Probed by Second Harmonic Generation , 2008 .

[18]  Chao Li,et al.  Self-assembled spiral nanoarchitecture and supramolecular chirality in Langmuir-Blodgett films of an achiral amphiphilic barbituric acid. , 2004, Journal of the American Chemical Society.

[19]  J. Byers,et al.  A second harmonic generation analog of optical rotatory dispersion for the study of chiral monolayers , 1994 .

[20]  Li Zhang,et al.  A Supramolecular Chiroptical Switch Exclusively from an Achiral Amphiphile , 2006 .

[21]  André Persoons,et al.  Second-order nonlinear optical properties of chiral materials , 2003 .

[22]  Jeffery J. Maki,et al.  Linearly polarized probes of surface chirality , 1995 .

[23]  Janice M. Hicks,et al.  Circular dichroism spectroscopy at interfaces: a surface second harmonic generation study , 1993 .

[24]  Daniel A. Higgins,et al.  Optical second harmonic generation as a probe of surface chemistry , 1994 .

[25]  J. Byers,et al.  Consequences of chirality in second-order non-linear spectroscopy at surfaces. , 1994, Faraday discussions.

[26]  Jaume Veciana,et al.  Homo- and Heterochiral Supramolecular Tapes from Achiral, Enantiopure, and Racemic Promesogenic Formamides: Expression of Molecular Chirality in Two and Three Dimensions. , 2001, Angewandte Chemie.

[27]  Y. Shen,et al.  Surface Second Harmonic Generation: A New Technique for Surface Studies , 1986 .

[28]  D Jacquemain,et al.  Crystallinity of the Double Layer of Cadmium Arachidate Films at the Water Surface , 1991, Science.