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Title: Intramolecular energy transfer with 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 andmore » solar cell applications.« less

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
967258
Report Number(s):
ANL/CSE/JA-60373
Journal ID: ISSN 0002-7863; JACSAT; TRN: US0904334
DOE Contract Number:  
DE-AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
J. Am. Chem. Soc.
Additional Journal Information:
Journal Volume: 130; Journal Issue: 13 ; 2008; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
ENGLISH
Subject:
14 SOLAR ENERGY; 43 PARTICLE ACCELERATORS; ABSORPTION SPECTROSCOPY; ANTENNAS; CHLOROPHYLL; DIMERS; ENERGY TRANSFER; EXCITONS; PHOTOSYNTHESIS; PORPHYRINS; PRISMS; ROTATION; SCATTERING; SOLAR CELLS; SYNCHROTRONS; SYNTHESIS; TOLUENE; TRANSIENTS; WAVELENGTHS

Citation Formats

Kelley, R F, Lee, S J, Wilson, T M, Nakamura, Y, Tiede, D M, Osuka, A, Hupp, J T, Wasielewski, M R, SUF-USR,, Chemical Sciences and Engineering Division, Northwestern Univ., and Kyoto Univ. Intramolecular energy transfer with butadiyne-linked chlorophyll and porphyrin dimer-faced, self-assembled prisms.. United States: N. p., 2008. Web. doi:10.1021/ja075494f.
Kelley, R F, Lee, S J, Wilson, T M, Nakamura, Y, Tiede, D M, Osuka, A, Hupp, J T, Wasielewski, M R, SUF-USR,, Chemical Sciences and Engineering Division, Northwestern Univ., & Kyoto Univ. Intramolecular energy transfer with butadiyne-linked chlorophyll and porphyrin dimer-faced, self-assembled prisms.. United States. https://doi.org/10.1021/ja075494f
Kelley, R F, Lee, S J, Wilson, T M, Nakamura, Y, Tiede, D M, Osuka, A, Hupp, J T, Wasielewski, M R, SUF-USR,, Chemical Sciences and Engineering Division, Northwestern Univ., and Kyoto Univ. 2008. "Intramolecular energy transfer with butadiyne-linked chlorophyll and porphyrin dimer-faced, self-assembled prisms.". United States. https://doi.org/10.1021/ja075494f.
@article{osti_967258,
title = {Intramolecular energy transfer with butadiyne-linked chlorophyll and porphyrin dimer-faced, self-assembled prisms.},
author = {Kelley, R F and Lee, S J and Wilson, T M and Nakamura, Y and Tiede, D M and Osuka, A and Hupp, J T and Wasielewski, M R and SUF-USR, and Chemical Sciences and Engineering Division and Northwestern Univ. and Kyoto Univ.},
abstractNote = {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.},
doi = {10.1021/ja075494f},
url = {https://www.osti.gov/biblio/967258}, journal = {J. Am. Chem. Soc.},
issn = {0002-7863},
number = 13 ; 2008,
volume = 130,
place = {United States},
year = {Tue Jan 01 00:00:00 EST 2008},
month = {Tue Jan 01 00:00:00 EST 2008}
}