title: Density-functional-theory investigation of conformations, 13C shielding, and magnetic field interactions in a V-shaped phenylene bis carboxylate homologous series.
abstract: Density functional theory (DFT) has been employed in a conformational study of a bent-core PBBC homologous series. IR spectra, GIAO-DFT chemical shielding tensors (CSTs), and molecular susceptibility tensors (MSTs) are theoretically calculated for various optimized conformations established by searching the potential energy surface of each PBBC V-shaped molecule. The IR results could aid the understanding of vibration normal modes, while the MST results can illuminate the alignment properties of the V-shaped molecules in an external magnetic field. CSTs of the aromatic carbons, and those previously measured by the 2D-NMR SUPER technique (with some (13)C NMR peaks reassigned for correctness based on new DFT calculations), were found to be in good agreement. These verified experimental CSTs are then used to revisit the (13)C NMR data to yield structural and local orientational order parameters for two members of the PBBC series. The PBBC series studied using the combined DFT-(13)C NMR approach strongly supports the notion that lesser populated conformational states found by DFT could be reached in the studied mesogens 10DClPBBC and 11ClPBBC upon decreasing temperature, as revealed by the change in the bend angle determined by NMR and identified with those of the DFT molecular structures optimized for various conformers.
authors: Dipartimento di Chimica e Chimica Industriale, Universitá di Pisa, via Risorgimento 35, I-56126 Pisa, Italy.
authors: Alberto
authors: A
authors: Marini
authors: Ronald Y
authors: RY
authors: Dong