title: Application of the perimeter model to the assignment of the electronic absorption spectra of gold(III) hexaphyrins with [4n+2] and [4n] pi-electron systems.
abstract: The electronic excited states of two forms of meso-hexakis(pentafluorophenyl)-substituted gold(III) hexaphyrin(1.1.1.1.1.1) have been investigated by density functional calculations and magnetic circular dichroism (MCD) spectroscopy, in order to assign their low-energy excited singlet states. We found that the perimeter model can be successfully applied to the interpretation of the electronic states. In the case of the neutral forms (Au(2)-N, Au-N), the absorption bands observed in the NIR and visible region can be assigned to pi-pi* transitions referred to as the L and B bands, respectively, analogous to the Q and Soret bands of regular porphyrins. In marked contrast with the neutral forms, the absorption bands of the reduced forms (Au(2)-R and Au-R) are attributed to pi-pi* transitions involving six frontier molecular pi orbitals. By applying the 4N-electron perimeter model, the six orbitals are labeled as h(-), h(+), s(-), s(+), l(-), and l(+), while the observed absorption bands can be assigned to the S, N(1), N(2), P(1), and P(2) transitions, in order of increasing energy.
authors.affiliation: Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578, Japan.
authors.forename: Atsuya
authors.initials: A
authors.lastname: Muranaka
authors.forename: Osamu
authors.initials: O
authors.lastname: Matsushita
authors.forename: Kengo
authors.initials: K
authors.lastname: Yoshida
authors.forename: Shigeki
authors.initials: S
authors.lastname: Mori
authors.forename: Masaaki
authors.initials: M
authors.lastname: Suzuki
authors.forename: Taniyuki
authors.initials: T
authors.lastname: Furuyama
authors.forename: Masanobu
authors.initials: M
authors.lastname: Uchiyama
authors.forename: Atsuhiro
authors.initials: A
authors.lastname: Osuka
authors.forename: Nagao
authors.initials: N
authors.lastname: Kobayashi