title: Intramolecular energy transfer within butadiyne-linked chlorophyll and porphyrin dimer-faced, self-assembled prisms.
abstract: The synthesis and photophysical properties of butadiyne-linked chlorophyll and porphyrin dimers in toluene solution and in several self-assembled prismatic structures are described. The butadiyne linkage between the 20-positions of the macrocycles results in new electronic transitions polarized along the long axes of the dimers. These transitions greatly increase the ability of these dimers to absorb the solar spectrum over a broad wavelength range. Femtosecond transient absorption spectroscopy reveals the relative rate of rotation of the macrocycles around the butadiyne bond joining them. Following addition of 3-fold symmetric, metal-coordinating ligands, both macrocyclic dimers self-assemble into prismatic structures in which the dimers comprise the faces of the prisms. These structures were confirmed by small-angle X-ray scattering experiments in solution using a synchrotron source. Photoexcitation of the prismatic assemblies reveals that efficient, through-space energy transfer occurs between the macrocyclic dimers within the prisms. The distance dependence of energy transfer between the faces of the prisms was observed by varying the size of the prismatic assemblies through the use of 3-fold symmetric ligands having arms with different lengths. These results show that self-assembly of discrete macrocyclic prisms provides a useful new strategy for controlling singlet exciton flow in antenna systems for artificial photosynthesis and solar cell applications.
authors.affiliation: Department of Chemistry and Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University, Evanston, Illinois 60208-3113, USA.
authors.forename: Richard F
authors.initials: RF
authors.lastname: Kelley
authors.forename: Suk Joong
authors.initials: SJ
authors.lastname: Lee
authors.forename: Thea M
authors.initials: TM
authors.lastname: Wilson
authors.forename: Yasuyuki
authors.initials: Y
authors.lastname: Nakamura
authors.forename: David M
authors.initials: DM
authors.lastname: Tiede
authors.forename: Atsuhiro
authors.initials: A
authors.lastname: Osuka
authors.forename: Joseph T
authors.initials: JT
authors.lastname: Hupp
authors.forename: Michael R
authors.initials: MR
authors.lastname: Wasielewski
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D002734:Chlorophyll / Q000138:chemical synthesis* / Q000737:chemistry*; D019281:Dimerization; D004735:Energy Transfer; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D010777:Photochemistry; D011166:Porphyrins / Q000138:chemical synthesis* / Q000737:chemistry*; D053838:Scattering, Small Angle; D014961:X-Ray Diffraction
chemical_list: D000480:Alkynes; D008024:Ligands; D011166:Porphyrins; D002734:Chlorophyll