title: Photoinduced electron transfer and nonlinear absorption in poly(carbazole-alt-2,7-fluorene)s bearing perylene diimides as pendant acceptors.
abstract: This paper reports the synthesis, photophysical behavior, and use in nanosecond optical-pulse suppression of a poly(2,7-carbazole-alt-2,7-fluorene) and a poly(3,6-carbazole-alt-2,7-fluorene) in which the carbazole N-positions are linked by an alkyl chain to one of the nitrogen atoms of a perylene-3,4,9,10-tetracarboxylic diimide (PDI) acceptor. It was found that the PDI pendants on the polymer side chain aggregated even in dilute solution, which extended the onset of PDI absorption into the near-infrared (NIR). Transient-absorption spectra of these polymers provide evidence for efficient electron transfer following either donor or acceptor photoexcitation to form long-lived charge-separated species, which exhibit strong absorption in the NIR. The spectral overlap between the transient species and the long-wavelength absorption edge of the aggregated PDI leads to reverse saturable absorption at 680 nm that can be used for optical-pulse suppression. Additionally, at high input energies, two-photon absorption mechanisms may also contribute to the suppression. PDI-grafted polymers exhibit enhanced optical-pulse suppression compared with blends of model materials composed of unfunctionalized poly(carbazole-alt-2,7-fluorene)s and PDI small molecules.
authors.affiliation: School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA.
authors.forename: Chun
authors.initials: C
authors.lastname: Huang
authors.forename: Matthew M
authors.initials: MM
authors.lastname: Sartin
authors.forename: Matteo
authors.initials: M
authors.lastname: Cozzuol
authors.forename: Nisan
authors.initials: N
authors.lastname: Siegel
authors.forename: Stephen
authors.initials: S
authors.lastname: Barlow
authors.forename: Joseph W
authors.initials: JW
authors.lastname: Perry
authors.forename: Seth R
authors.initials: SR
authors.lastname: Marder
mesh_terms: D002227:Carbazoles / Q000138:chemical synthesis / Q000737:chemistry*; D004579:Electron Transport; D005449:Fluorenes / Q000138:chemical synthesis / Q000737:chemistry*; D007094:Imides / Q000737:chemistry*; D015394:Molecular Structure; D010569:Perylene / Q000031:analogs & derivatives* / Q000737:chemistry; D055668:Photochemical Processes
chemical_list: D002227:Carbazoles; D005449:Fluorenes; D007094:Imides; C521332:perylenediimide; D010569:Perylene