The Effect of the π-Electron        Delocalization Curvature on the       Two-Photon Circular Dichroism of         Molecul...
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Jpcl 10.1021 jz300577 hernández presentation

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The Effect of the π-Electron Delocalization Curvature on the Two-Photon Circular Dichroism of Molecules with Axial Chirality

Herein we report on the theoretical-experimental study of the effect of curvature of the π-electron delocalization on the two-photon circular dichroism (TPCD) of a family of optically active biaryl derivatives (S-BINOL, S-VANOL, and S-VAPOL). The comparative analysis of the influence of the different transition moments to their corresponding TPCD rotatory strength reveals an enhanced contribution of the magnetic transition dipole moment on VAPOL. This effect is hereby attributed to the additional twist in the π–electron delocalization on this compound. TPCD measurements were done using the double L-scan technique in the picosecond regime. Theoretical calculations were completed using modern analytical response theory, within a time-dependent density functional theory (TD-DFT) approach, at both, B3LYP and CAM-B3LYP levels, with the aug-cc-pVDZ basis set for S-BINOL and S-VANOL, and 6-31G* for S-VAPOL. Solvent effects were included by means of the polarizable continuum model (PCM) in CH2Cl2.

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Jpcl 10.1021 jz300577 hernández presentation

  1. 1. The Effect of the π-Electron Delocalization Curvature on the Two-Photon Circular Dichroism of Molecules with Axial Chirality Carlos Diaz,† Na Lin,‡,§ Carlos Toro,† Remy Passier,† Antonio Rizzo,∥ and Florencio E. Hernandez†,⊥† Department of Chemistry, University of Central Florida‡ State Key Laboratory of Crystal Materials, Shandong University, China§Department of Chemistry, University of Tromsø, N-9037 Tromsø, Norway∥ Consiglio Nazionale delle Ricerche, Istituto per i Processi Chimico Fisici, Italy⊥The College of Optics and Photonics, CREOL University of Central Florida J. Phys. Chem. Lett. 2012, 3, 1808-1813 1
  2. 2. MotivationThe understanding of chiral moleculeswith major relevance inbiology, pharmacology, catalysis, nanotechnology, optics and photonics. Limitations of ECD: • Dark in the far UV. Advantages of TPCD: • Allows access into an unexplored spectral UV region. Proprietary and Confidential 2 American Chemical Society
  3. 3. Theoretical-Experimental Approach TPCD was theoretically TPCD was revisited and predicted in 1975. expanded in 2006. Double L-scan Technique J. Chem. Phys. 1975, 62, 1006. //J. Chem. Phys. 1975, 63, 1348. Opt. Lett. 2008, 33, 2958. J. Chem.Phys., 2006 , 125, 064113. Chem. Eur. J. 2010, 16, 3504Proprietary and Confidential 3American Chemical Society
  4. 4. Definition of TPCD 2 TPCD L R 4 2 g 2 NA TPCD 2 2 3 2 R0 f 0f 15 c0 4 0 1 TPCD TI TI TI R 0f 0f bB 1 1 0f bB2 2 0f bB 3 3 0f 1 B1TI 0f 3 M p ,0 f 0f P p*,0 f 0f 1 TI B2 0f 3 T ,0 f 0f P p*,0 f 0f 2 2 TI 1 B3 0f 3 M p ,0 f 0f P p*,0 f 0f J. Chem. Phys. 1975, 62, 1006. //J. Chem. Phys. 1975, 63, 1348. J. Chem.Phys., 2006 , 125, 064113.Proprietary and Confidential 4American Chemical Society
  5. 5. S-BINOL, S-VANOL and S-VAPOL( -electron delocalization direction) TPCD was measured on these three compounds to understand the effect of conjugation direction and extension.Proprietary and Confidential 5American Chemical Society
  6. 6. Two-Photon Absorption (TPA) andTPCD spectra S-BINOL S-VANOL S-VAPOLProprietary and Confidential 6American Chemical Society
  7. 7. Contributions to RTPCD from thedifferent transition moments Electric transition quadrupole moment contributions Magnetic transition dipole moment contributions J.C.S. Faraday II, 1980, 76, 1249. Phys. Rev. A 2007, 75, 032518.Proprietary and Confidential 7American Chemical Society
  8. 8. F. E. Hernandez A. Rizzo C. Diaz N. Lin C. Toro R. PassierGrant Number CHE-0832622Proprietary and Confidential 8American Chemical Society

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