title: Suppression of HOMO-LUMO transition in a twist form of oligo(phenyleneethynylene) clamped by a right-handed helical peptide.
abstract: A donor-π-acceptor (D-π-A) system of oligo(phenyleneethynylene) (OPE) was twisted by clamping both ends of the OPE with a right-handed helical peptide (SSA8=OPE). The induced twist in OPE was in a right-handed way. SSA8=OPE showed a weaker HOMO-LUMO band in the absorption spectrum than that of a reference compound AcOPE without the helix bridge. The fluorescence quantum yield of SSA8=OPE was extremely low (0.0045-0.0165), which was in contrast to AcOPE with a moderate quantum yield of 0.355. The fluorescence life times of SSA8=OPE and AcOPE were nearly the same. Time-dependent density functional theory calculations (b3lyp/6-31G(d,p) level) on a twisted conformation of the D-π-A system qualitatively reproduced CD spectra and UV spectra of a weak oscillator strength of the HOMO-LUMO transition. Upon twisting the D-π-A system, the oscillator strength of the HOMO-LUMO transition is thus reduced.
authors.affiliation: Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto-Daigaku-Katsura, Kyoto 615-8510, Japan.
authors.forename: Hidenori
authors.initials: H
authors.lastname: Nakayama
authors.forename: Shunsaku
authors.initials: S
authors.lastname: Kimura
mesh_terms: D000042:Absorption; D000480:Alkynes / Q000737:chemistry*; D002942:Circular Dichroism; D004987:Ethers / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D010455:Peptides / Q000737:chemistry*; D011789:Quantum Theory; D013056:Spectrophotometry, Ultraviolet
chemical_list: D000480:Alkynes; D004987:Ethers; D010455:Peptides; C436384:phenyleneethynylene