Excitation energy migration processes in various multi-porphyrin assemblies

Jaesung Yang, Dongho Kim

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8 Citations (Scopus)

Abstract

The electronic interactions and excitation energy transfer (EET) processes of a variety of multi-porphyrin arrays with linear, cyclic and box architectures have been explored. Directly meso-meso linked linear arrays (ZN ) exhibit strong excitonic coupling with an exciton coherence length of approximately 6 porphyrin units, while fused linear arrays (TN ) exhibit extensive π-conjugation over the whole array. The excitonic coherence length in directly linked cyclic porphyrin rings (CZN ) was determined to be approximately 2.7 porphyrin units by simultaneous analysis of fluorescence intensities and lifetimes at the single-molecule level. By performing transient absorption (TA) and TA anisotropy decay measurements, the EET rates in m-phenylene linked cyclic porphyrin wheels C12ZA and C24ZB were determined to be 4 and 36 ps -1, respectively. With increasing the size of CNZA, the EET efficiencies decrease owing to the structural distortions that produce considerable non-radiative decay pathways. Finally, the EET rates of self-assembled porphyrin boxes consisting of directly linked diporphyrins, B1A, B2A and B3A, are 48, 98 and 361 ps-1, respectively. The EET rates of porphyrin boxes consisting of alkynylenebridged diporphyrins, B2B and B4B, depend on the conformation of building blocks (planar or orthogonal) rather than the length of alkynylene linkers.

Original languageEnglish
Pages (from-to)3802-3818
Number of pages17
JournalPhilosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences
Volume370
Issue number1972
DOIs
Publication statusPublished - 2012 Aug 13

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Porphyrin
Excitation energy
Porphyrins
porphyrins
assemblies
Migration
Excitation
Energy Transfer
Energy transfer
energy transfer
Energy
excitation
boxes
Linear Array
linear arrays
energy
Absorption
Decay
Unit
Exciton

All Science Journal Classification (ASJC) codes

  • Mathematics(all)
  • Engineering(all)
  • Physics and Astronomy(all)

Cite this

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abstract = "The electronic interactions and excitation energy transfer (EET) processes of a variety of multi-porphyrin arrays with linear, cyclic and box architectures have been explored. Directly meso-meso linked linear arrays (ZN ) exhibit strong excitonic coupling with an exciton coherence length of approximately 6 porphyrin units, while fused linear arrays (TN ) exhibit extensive π-conjugation over the whole array. The excitonic coherence length in directly linked cyclic porphyrin rings (CZN ) was determined to be approximately 2.7 porphyrin units by simultaneous analysis of fluorescence intensities and lifetimes at the single-molecule level. By performing transient absorption (TA) and TA anisotropy decay measurements, the EET rates in m-phenylene linked cyclic porphyrin wheels C12ZA and C24ZB were determined to be 4 and 36 ps -1, respectively. With increasing the size of CNZA, the EET efficiencies decrease owing to the structural distortions that produce considerable non-radiative decay pathways. Finally, the EET rates of self-assembled porphyrin boxes consisting of directly linked diporphyrins, B1A, B2A and B3A, are 48, 98 and 361 ps-1, respectively. The EET rates of porphyrin boxes consisting of alkynylenebridged diporphyrins, B2B and B4B, depend on the conformation of building blocks (planar or orthogonal) rather than the length of alkynylene linkers.",
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AU - Kim, Dongho

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AB - The electronic interactions and excitation energy transfer (EET) processes of a variety of multi-porphyrin arrays with linear, cyclic and box architectures have been explored. Directly meso-meso linked linear arrays (ZN ) exhibit strong excitonic coupling with an exciton coherence length of approximately 6 porphyrin units, while fused linear arrays (TN ) exhibit extensive π-conjugation over the whole array. The excitonic coherence length in directly linked cyclic porphyrin rings (CZN ) was determined to be approximately 2.7 porphyrin units by simultaneous analysis of fluorescence intensities and lifetimes at the single-molecule level. By performing transient absorption (TA) and TA anisotropy decay measurements, the EET rates in m-phenylene linked cyclic porphyrin wheels C12ZA and C24ZB were determined to be 4 and 36 ps -1, respectively. With increasing the size of CNZA, the EET efficiencies decrease owing to the structural distortions that produce considerable non-radiative decay pathways. Finally, the EET rates of self-assembled porphyrin boxes consisting of directly linked diporphyrins, B1A, B2A and B3A, are 48, 98 and 361 ps-1, respectively. The EET rates of porphyrin boxes consisting of alkynylenebridged diporphyrins, B2B and B4B, depend on the conformation of building blocks (planar or orthogonal) rather than the length of alkynylene linkers.

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