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Two-Photon Polarization Dependent Spectroscopy in Chirality: A Novel Experimental-Theoretical Approach to Study Optically Active Systems
Department of Chemistry, University of Central Florida, P. O. Box 162366, Orlando, FL 382616, USA
The College of Optics and Photonics, CREOL University of Central Florida, P. O. Box 162366, Orlando, FL 382616, USA
Consiglio Nazionale delle Ricerche (CNR), Istituto per i Processi Chimico Fisici (IPCF-CNR), UoS di Pisa, Area della Ricerca, Via G. Moruzzi 1, I-56124 Pisa, Italy
* Author to whom correspondence should be addressed.
Received: 2 March 2011; in revised form: 7 April 2011 / Accepted: 12 April 2011 / Published: 18 April 2011
Abstract: Many phenomena, including life itself and its biochemical foundations are fundamentally rooted in chirality. Combinatorial methodologies for catalyst discovery and optimization remain an invaluable tool for gaining access to enantiomerically pure compounds in the development of pharmaceuticals, agrochemicals, and flavors. Some exotic metamaterials exhibiting negative refractive index at optical frequencies are based on chiral structures. Chiroptical activity is commonly quantified in terms of circular dichroism (CD) and optical rotatory dispersion (ORD). However, the linear nature of these effects limits their application in the far and near-UV region in highly absorbing and scattering biological systems. In order to surmount this barrier, in recent years we made important advancements on a novel non linear, low-scatter, long-wavelength CD approach called two-photon absorption circular dichroism (TPACD). Herein we present a descriptive analysis of the optics principles behind the experimental measurement of TPACD, i.e., the double L-scan technique, and its significance using pulsed lasers. We also make an instructive examination and discuss the reliability of our theoretical-computational approach, which uses modern analytical response theory, within a Time-Dependent Density Functional Theory (TD-DFT) approach. In order to illustrate the potential of this novel spectroscopic tool, we first present the experimental and theoretical results obtained in C2-symmetric, axially chiral R-(+)-1,1'-bi(2-naphthol), R-BINOL, a molecule studied at the beginning of our investigation in this field. Next, we reveal some preliminary results obtained for (R)-3,3′-diphenyl-2,2′-bi-1-naphthol, R-VANOL, and (R)-2,2′-diphenyl-3,3′-(4-biphenanthrol), R-VAPOL. This family of optically active compounds has been proven to be a suitable model for the structure-property relationship study of TPACD, because its members are highly conjugated yet photo-stable, and easily derivatized at the 5- and 6-positions. With the publication of these outcomes we hope to motivate more members of the scientist community to engage in state-of-the-art TPACD spectroscopy.
Keywords: Non-linear spectroscopy; circular dichroism; two-photon absorption; chirality; bi-naphthols
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MDPI and ACS Style
Hernández, F.E.; Rizzo, A. Two-Photon Polarization Dependent Spectroscopy in Chirality: A Novel Experimental-Theoretical Approach to Study Optically Active Systems. Molecules 2011, 16, 3315-3337.
Hernández FE, Rizzo A. Two-Photon Polarization Dependent Spectroscopy in Chirality: A Novel Experimental-Theoretical Approach to Study Optically Active Systems. Molecules. 2011; 16(4):3315-3337.
Hernández, Florencio E.; Rizzo, Antonio. 2011. "Two-Photon Polarization Dependent Spectroscopy in Chirality: A Novel Experimental-Theoretical Approach to Study Optically Active Systems." Molecules 16, no. 4: 3315-3337.