title: Weakly coupled molecular photonic wires: synthesis and excited-state energy-transfer dynamics.
abstract: Molecular photonic wires, which absorb light and undergo excited-state energy transfer, are of interest as biomimetic models for photosynthetic light-harvesting systems and as molecular devices with potential applications in materials chemistry. We describe the stepwise synthesis of four molecular photonic wires. Each wire consists of an input unit, transmission element, and output unit. The input unit consists of a boron-dipyrrin dye or a perylene-monoimide dye (linked either at the N-imide or the C9 position); the transmission element consists of one or three zinc porphyrins affording short or long wires, respectively; and the output unit consists of a free base (Fb) porphyrin. The components in the arrays are joined in a linear architecture via diarylethyne linkers (an ethynylphenyl linker is attached to the C9-linked perylene). The wires have been examined by static absorption, static fluorescence, and time-resolved absorption spectroscopy. Each wire (with the exception of the C9-linked perylene wire) exhibits a visible absorption spectrum that is the sum of the spectra of the component parts, indicating the relatively weak electronic coupling between the components. Excitation of each wire at the wavelength where the input unit absorbs preferentially (typically 480-520 nm) results in emission almost exclusively from the Fb porphyrin. The static emission and time-resolved data indicate that the overall rate constants and quantum efficiencies for end-to-end (i.e., input to output) energy transfer are as follows: perylene-(N-imide)-linked short wire, (33 ps)(-1) and >99%; perylene-(C9)-linked short wire, (26 ps)(-1) and >99%; boron-dipyrrin-based long wire, (190 ps)(-1) and 81%; perylene-(N-imide)-linked long wire, (175 ps)(-1) and 86%. Collectively, the studies provide valuable insight into the singlet-singlet excited-state energy-transfer properties in weakly coupled molecular photonic wires.
authors.affiliation: Department of Chemistry, North Carolina State University, Raleigh, NC 27695-8204, USA.
authors.forename: Arounaguiry
authors.initials: A
authors.lastname: Ambroise
authors.forename: Christine
authors.initials: C
authors.lastname: Kirmaier
authors.forename: Richard W
authors.initials: RW
authors.lastname: Wagner
authors.forename: Robert S
authors.initials: RS
authors.lastname: Loewe
authors.forename: David F
authors.initials: DF
authors.lastname: Bocian
authors.forename: Dewey
authors.initials: D
authors.lastname: Holten
authors.forename: Jonathan S
authors.initials: JS
authors.lastname: Lindsey
mesh_terms: D004396:Coloring Agents / Q000737:chemistry; D004735:Energy Transfer; D007094:Imides / Q000737:chemistry; D008665:Metalloporphyrins / Q000138:chemical synthesis / Q000737:chemistry*; D010569:Perylene / Q000737:chemistry*; D017785:Photons
chemical_list: D004396:Coloring Agents; D007094:Imides; D008665:Metalloporphyrins; C017802:zinc hematoporphyrin; D010569:Perylene