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.
†Department of Chemistry, University of Central Florida, P.O. Box 162366, Orlando, Florida 382616-2366, United States.
Carlos
C
Diaz
‡State Key Laboratory of Crystal Materials, Shandong University, 250100 Jinan, Shandong, People's Republic of China.|§Center for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø, N-9037 Tromsø, Norway.
Na
N
Lin
†Department of Chemistry, University of Central Florida, P.O. Box 162366, Orlando, Florida 382616-2366, United States.
Carlos
C
Toro
†Department of Chemistry, University of Central Florida, P.O. Box 162366, Orlando, Florida 382616-2366, United States.
Remy
R
Passier
∥CNR - Consiglio Nazionale delle Ricerche, Istituto per i Processi Chimico Fisici (IPCF-CNR), UoS di Pisa, Area della Ricerca, Via G. Moruzzi 1, I-56124 Pisa, Italy.
Antonio
A
Rizzo
†Department of Chemistry, University of Central Florida, P.O. Box 162366, Orlando, Florida 382616-2366, United States.|⊥The College of Optics and Photonics, CREOL University of Central Florida, P.O. Box 162366, Orlando, Florida 382616-2366, United States.
Florencio E
FE
Hernández
biaryl derivatives; circular polarization; magnetic transition dipole moment; molecular currents; nonlinear rotatory strength