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Presentation jpc letters eh1 cd1 Presentation jpc letters eh1 cd1 Presentation Transcript

  • 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. ndez†,⊥† 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
  • 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
  • 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 View slide
  • 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 View slide
  • 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
  • Two-Photon Absorption (TPA) andTPCD spectra S-BINOL S-VANOL S-VAPOLProprietary and Confidential 6American Chemical Society
  • 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
  • F. E. Hernandez A. Rizzo C. Diaz N. Lin C. Toro R. PassierGrant Number CHE-0832622Proprietary and Confidential 8American Chemical Society