Directly linked porphyrin arrays with tunable excitonic interactions

Dongho Kim, Atsuhiro Osuka

Research output: Contribution to journalArticle

373 Citations (Scopus)

Abstract

On the basis of the Ag(I)-promoted coupling reaction of Zn(II) 5,-15-diaryl porphyrin that gave a meso-meso-linked diporphyrin, we developed a variety of directly linked porphyrin arrays including linear, windmill, gridlike, cyclic, and box architectures. Electronic and excitonic interactions are thus fine tuned by placing porphyrin chromophores in well-defined arrangements. Photoexcited-state dynamics of these porphyrin arrays, as revealed by various ultrafast laser-based measurements, are pertinent to photosynthetic light-harvesting antenna in terms of very efficient excitation energy hopping over many porphyrins and lack of a defect that acts as energy sink. The conformational flexibility of a meso-meso-linked diporphyrin has also been used for the fine tuning of excitonic interactions as demonstrated by strapped meso-meso diporphyrins and reversible switching of energy transfer in a triporphyrin. Triply linked porphyrin arrays have also been explored, which exhibit an exceptionally low HOMO-LUMO gap as a result of a fully conjugated π electronic system over a coplanar platform.

Original languageEnglish
Pages (from-to)735-745
Number of pages11
JournalAccounts of Chemical Research
Volume37
Issue number10
DOIs
Publication statusPublished - 2004 Oct 1

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Porphyrins
Ultrafast lasers
Excitation energy
Chromophores
Energy transfer
Tuning
Antennas
Defects

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

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abstract = "On the basis of the Ag(I)-promoted coupling reaction of Zn(II) 5,-15-diaryl porphyrin that gave a meso-meso-linked diporphyrin, we developed a variety of directly linked porphyrin arrays including linear, windmill, gridlike, cyclic, and box architectures. Electronic and excitonic interactions are thus fine tuned by placing porphyrin chromophores in well-defined arrangements. Photoexcited-state dynamics of these porphyrin arrays, as revealed by various ultrafast laser-based measurements, are pertinent to photosynthetic light-harvesting antenna in terms of very efficient excitation energy hopping over many porphyrins and lack of a defect that acts as energy sink. The conformational flexibility of a meso-meso-linked diporphyrin has also been used for the fine tuning of excitonic interactions as demonstrated by strapped meso-meso diporphyrins and reversible switching of energy transfer in a triporphyrin. Triply linked porphyrin arrays have also been explored, which exhibit an exceptionally low HOMO-LUMO gap as a result of a fully conjugated π electronic system over a coplanar platform.",
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Directly linked porphyrin arrays with tunable excitonic interactions. / Kim, Dongho; Osuka, Atsuhiro.

In: Accounts of Chemical Research, Vol. 37, No. 10, 01.10.2004, p. 735-745.

Research output: Contribution to journalArticle

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