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
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
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
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