Synthesis and Excited-State Photodynamics of a Molecular Square Containing Four Mutually Coplanar Porphyrins

Richard W. Wagner, Jyoti Seth, Sung Ik Yang, Dongho Kim, David F. Bocian, Dewey Holten, Jonathan S. Lindsey

Research output: Contribution to journalArticle

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Abstract

To examine the effect of restricted porphyrin-porphyrin rotation on energy transfer in diphenylethyne-linked porphyrin arrays, a square macrocyclic array of four porphyrins has been prepared that locks the porphyrins in a mutually coplanar architecture. The palladium-mediated coupling of Zn(II) 5,10-dimesityl-15,20-bis(4-ethynylphenyl)porphyrin and 5,10-dimesityl-15,20-bis(4-iodophenyl)porphyrin afforded the molecular square (cyclo-Zn2Fb2U) with zinc (Zn) and free base (Fb) porphyrins on alternating corners. The yield of cyclo-Zn2Fb2U is relatively insensitive to concentration with reactants at 5-0.5 mM but declines significantly at <0.05 mM. Transient absorption data from cyclo-Zn2Fb2U in toluene at room temperature indicate that the rate of energy transfer from the photoexcited Zn porphyrin to a neighboring Fb porphyrin is (26 ps)-1. A ZnFb porphyrin (ZnFbU) with an identical diphenylethyne linker but no constraints on rotation exhibits an identical energy-transfer rate. Resonance Raman spectroscopy shows that the intensities of the νC≡C mode(s) of the cyclo-Zn2Fb2U are comparable to those of ZnFbU, indicating that the extent of electronic coupling between the ethyne groups and the π-systems of the porphyrins is comparable in the two types of arrays. Thus, the geometric constraints imposed by the closure to the macrocyclic structure, including the enforced coplanarity of the four porphyrin rings, do not alter the through-bond electronic communication among the porphyrins.

Original languageEnglish
Pages (from-to)5042-5049
Number of pages8
JournalJournal of Organic Chemistry
Volume63
Issue number15
DOIs
Publication statusPublished - 1998 Jul 24

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Porphyrins
Excited states
Energy transfer
Zinc
Acetylene
Toluene
Palladium
Raman spectroscopy

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

Cite this

Wagner, Richard W. ; Seth, Jyoti ; Yang, Sung Ik ; Kim, Dongho ; Bocian, David F. ; Holten, Dewey ; Lindsey, Jonathan S. / Synthesis and Excited-State Photodynamics of a Molecular Square Containing Four Mutually Coplanar Porphyrins. In: Journal of Organic Chemistry. 1998 ; Vol. 63, No. 15. pp. 5042-5049.
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abstract = "To examine the effect of restricted porphyrin-porphyrin rotation on energy transfer in diphenylethyne-linked porphyrin arrays, a square macrocyclic array of four porphyrins has been prepared that locks the porphyrins in a mutually coplanar architecture. The palladium-mediated coupling of Zn(II) 5,10-dimesityl-15,20-bis(4-ethynylphenyl)porphyrin and 5,10-dimesityl-15,20-bis(4-iodophenyl)porphyrin afforded the molecular square (cyclo-Zn2Fb2U) with zinc (Zn) and free base (Fb) porphyrins on alternating corners. The yield of cyclo-Zn2Fb2U is relatively insensitive to concentration with reactants at 5-0.5 mM but declines significantly at <0.05 mM. Transient absorption data from cyclo-Zn2Fb2U in toluene at room temperature indicate that the rate of energy transfer from the photoexcited Zn porphyrin to a neighboring Fb porphyrin is (26 ps)-1. A ZnFb porphyrin (ZnFbU) with an identical diphenylethyne linker but no constraints on rotation exhibits an identical energy-transfer rate. Resonance Raman spectroscopy shows that the intensities of the νC≡C mode(s) of the cyclo-Zn2Fb2U are comparable to those of ZnFbU, indicating that the extent of electronic coupling between the ethyne groups and the π-systems of the porphyrins is comparable in the two types of arrays. Thus, the geometric constraints imposed by the closure to the macrocyclic structure, including the enforced coplanarity of the four porphyrin rings, do not alter the through-bond electronic communication among the porphyrins.",
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Synthesis and Excited-State Photodynamics of a Molecular Square Containing Four Mutually Coplanar Porphyrins. / Wagner, Richard W.; Seth, Jyoti; Yang, Sung Ik; Kim, Dongho; Bocian, David F.; Holten, Dewey; Lindsey, Jonathan S.

In: Journal of Organic Chemistry, Vol. 63, No. 15, 24.07.1998, p. 5042-5049.

Research output: Contribution to journalArticle

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AU - Wagner, Richard W.

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