title: One- and two-photon absorptions in asymmetrically substituted free-base porphyrins: a density functional theory study.
abstract: Electronic spectra and structures of a new family of free-base porphyrin (H(2)P) derivatives with 4-(diphenylamino)stilbene (DPAS) or 4,4'-bis-(diphenylamino)stilbene (BDPAS) asymmetric substituents, recently synthesized and studied by Drobizhev et al. [J. Phys. Chem. B 110, 9802 (2006)] are investigated by density functional theory (DFT) using modern density functionals and the 6-31G* basis set. The time-dependent DFT technique is applied for calculations of one- and two-photon absorption spectra, electric and magnetic dipole moments, and for prediction of electronic circular dichroism for these chiral molecules. The four-band absorption spectrum of the H(2)P molecule (Q(x), Q(y), 0-0 and 1-0 bands) is enhanced in single-bond-linked DPAS. This enhancement is explained by hyperconjugation of the almost orthogonal pi systems and by small charge-transfer admixtures. The effect is much stronger for the double-bond- and triple-bond-linked DPAS and BDPAS substituents where absorption in the Q region transforms into a two-band spectrum. These molecules with ethenyl and ethynyl bonding of the porphyrin and donor substituent show very strong two-photon absorption in the near-infrared region. DFT calculations explain this by more efficient conjugation between the H(2)P and DPAS (BDPAS) chromophores, since they are almost coplanar: "Gerade" states of the H(2)P molecule occur in the Soret region and transform into charge-transfer states with nonzero transition moments. They are responsible for the strong two-photon absorption effects. Mixing of excitations in both chromophores explains the broadening of the Soret band. Though the calculated two-photon absorption cross sections are overestimated, the qualitative trends are reproduced and help understanding the whole genesis of spectra of these asymmetrically substituted H(2)P derivatives.
authors.affiliation: Theoretical Chemistry, Royal Institute of Technology, AlbaNova, Stockholm, Sweden. prakash@theochem.kth.se
authors.forename: Prakash
authors.initials: P
authors.lastname: Chandra Jha
authors.forename: Boris
authors.initials: B
authors.lastname: Minaev
authors.forename: Hans
authors.initials: H
authors.lastname: Agren
mesh_terms: D000042:Absorption; D003198:Computer Simulation; D036641:Microscopy, Fluorescence, Multiphoton / Q000379:methods*; D008956:Models, Chemical; D008958:Models, Molecular; D017785:Photons; D011166:Porphyrins / Q000737:chemistry* / Q000528:radiation effects*
chemical_list: D011166:Porphyrins