Design, synthesis, and photodynamics of light-harvesting arrays comprised of a porphyrin and one, two, or eight boron-dipyrrin accessory pigments

Feirong Li, Sung Ik Yang, Yangzhen Ciringh, Jyoti Seth, Charles H. Martin, Deepak L. Singh, Dongho Kim, Robert R. Birge, David F. Bocian, Dewey Holten, Jonathan S. Lindsey

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Abstract

Light-harvesting arrays containing one, two, or eight boron-dipyrrin (BDPY) pigments and one porphyrin (free base or Zn chelate) have been synthesized using a modular building block approach. The reaction of pyrrole and 4-(BDPY)benzaldehyde or 3,5-bis(BDPY)benzaldehyde, prepared by Pd- mediated ethynylation with the corresponding iodo-benzaldehydes, affords the desired BDPY-porphyrin array in yields of 10-58%. The arrays are soluble in organic solvents and have been characterized by static and time-resolved absorption and fluorescence spectroscopy. The blue-green BDPY absorption complements spectral coverage of the porphyrin chromophores and rivals the intensity of the porphyrin Soret band when eight BDPY accessory pigments are present. Efficient energy transfer from the BDPY pigment(s) to the porphyrin (free base or Zn-chelate) is observed in arrays containing one or two (>90%) or eight (>85%) accessory pigments per porphyrin. Biphasic excited-state decay behavior is exhibited by the BDPY pigments in isolated form and in the arrays. The time constants are ~15 and ~500 ps in the reference compounds (both reflecting deactivation to the ground state) and ~2 and ~20 ps in the arrays (both primarily reflecting energy transfer to the porphyrin). The longer-lived kinetic component comprises ~70% of the decay in each case. Ab initio calculations suggest that the two kinetic components are associated with two energetically accessible excited-state conformers involving the boron-dipyrrin unit and the 5-aryl ring (which is integral to the linker in the arrays). The calculations and experimental results indicate that the two excited-state conformers differ from one another in structure (the planarity of the boron-dipyrrin unit and its orientation with respect to the 5-aryl ring), electronic composition (especially the electron density on the 5-aryl group of the boron-dipyrrin unit), radiative and nonradiative coupling to the ground state, and the rate of energy transfer to the porphyrin constituent in the arrays. The high energy-transfer efficiencies together with favorable light-absorption and chemical properties exhibited by the boron-dipyrrin pigments make them amenable for use in porphyrin-based arrays for molecular photonics applications.

Original languageEnglish
Pages (from-to)10001-10017
Number of pages17
JournalJournal of the American Chemical Society
Volume120
Issue number39
DOIs
Publication statusPublished - 1998 Oct 7

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Boron
Porphyrins
Accessories
Pigments
Light
Energy Transfer
Energy transfer
Excited states
Ground state
Benzaldehydes
Optics and Photonics
Pyrroles
Kinetics
Fluorescence Spectrometry
Fluorescence spectroscopy
Chromophores
Absorption spectroscopy
Organic solvents
Photonics
Light absorption

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Li, Feirong ; Yang, Sung Ik ; Ciringh, Yangzhen ; Seth, Jyoti ; Martin, Charles H. ; Singh, Deepak L. ; Kim, Dongho ; Birge, Robert R. ; Bocian, David F. ; Holten, Dewey ; Lindsey, Jonathan S. / Design, synthesis, and photodynamics of light-harvesting arrays comprised of a porphyrin and one, two, or eight boron-dipyrrin accessory pigments. In: Journal of the American Chemical Society. 1998 ; Vol. 120, No. 39. pp. 10001-10017.
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abstract = "Light-harvesting arrays containing one, two, or eight boron-dipyrrin (BDPY) pigments and one porphyrin (free base or Zn chelate) have been synthesized using a modular building block approach. The reaction of pyrrole and 4-(BDPY)benzaldehyde or 3,5-bis(BDPY)benzaldehyde, prepared by Pd- mediated ethynylation with the corresponding iodo-benzaldehydes, affords the desired BDPY-porphyrin array in yields of 10-58{\%}. The arrays are soluble in organic solvents and have been characterized by static and time-resolved absorption and fluorescence spectroscopy. The blue-green BDPY absorption complements spectral coverage of the porphyrin chromophores and rivals the intensity of the porphyrin Soret band when eight BDPY accessory pigments are present. Efficient energy transfer from the BDPY pigment(s) to the porphyrin (free base or Zn-chelate) is observed in arrays containing one or two (>90{\%}) or eight (>85{\%}) accessory pigments per porphyrin. Biphasic excited-state decay behavior is exhibited by the BDPY pigments in isolated form and in the arrays. The time constants are ~15 and ~500 ps in the reference compounds (both reflecting deactivation to the ground state) and ~2 and ~20 ps in the arrays (both primarily reflecting energy transfer to the porphyrin). The longer-lived kinetic component comprises ~70{\%} of the decay in each case. Ab initio calculations suggest that the two kinetic components are associated with two energetically accessible excited-state conformers involving the boron-dipyrrin unit and the 5-aryl ring (which is integral to the linker in the arrays). The calculations and experimental results indicate that the two excited-state conformers differ from one another in structure (the planarity of the boron-dipyrrin unit and its orientation with respect to the 5-aryl ring), electronic composition (especially the electron density on the 5-aryl group of the boron-dipyrrin unit), radiative and nonradiative coupling to the ground state, and the rate of energy transfer to the porphyrin constituent in the arrays. The high energy-transfer efficiencies together with favorable light-absorption and chemical properties exhibited by the boron-dipyrrin pigments make them amenable for use in porphyrin-based arrays for molecular photonics applications.",
author = "Feirong Li and Yang, {Sung Ik} and Yangzhen Ciringh and Jyoti Seth and Martin, {Charles H.} and Singh, {Deepak L.} and Dongho Kim and Birge, {Robert R.} and Bocian, {David F.} and Dewey Holten and Lindsey, {Jonathan S.}",
year = "1998",
month = "10",
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doi = "10.1021/ja9812047",
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Li, F, Yang, SI, Ciringh, Y, Seth, J, Martin, CH, Singh, DL, Kim, D, Birge, RR, Bocian, DF, Holten, D & Lindsey, JS 1998, 'Design, synthesis, and photodynamics of light-harvesting arrays comprised of a porphyrin and one, two, or eight boron-dipyrrin accessory pigments', Journal of the American Chemical Society, vol. 120, no. 39, pp. 10001-10017. https://doi.org/10.1021/ja9812047

Design, synthesis, and photodynamics of light-harvesting arrays comprised of a porphyrin and one, two, or eight boron-dipyrrin accessory pigments. / Li, Feirong; Yang, Sung Ik; Ciringh, Yangzhen; Seth, Jyoti; Martin, Charles H.; Singh, Deepak L.; Kim, Dongho; Birge, Robert R.; Bocian, David F.; Holten, Dewey; Lindsey, Jonathan S.

In: Journal of the American Chemical Society, Vol. 120, No. 39, 07.10.1998, p. 10001-10017.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Design, synthesis, and photodynamics of light-harvesting arrays comprised of a porphyrin and one, two, or eight boron-dipyrrin accessory pigments

AU - Li, Feirong

AU - Yang, Sung Ik

AU - Ciringh, Yangzhen

AU - Seth, Jyoti

AU - Martin, Charles H.

AU - Singh, Deepak L.

AU - Kim, Dongho

AU - Birge, Robert R.

AU - Bocian, David F.

AU - Holten, Dewey

AU - Lindsey, Jonathan S.

PY - 1998/10/7

Y1 - 1998/10/7

N2 - Light-harvesting arrays containing one, two, or eight boron-dipyrrin (BDPY) pigments and one porphyrin (free base or Zn chelate) have been synthesized using a modular building block approach. The reaction of pyrrole and 4-(BDPY)benzaldehyde or 3,5-bis(BDPY)benzaldehyde, prepared by Pd- mediated ethynylation with the corresponding iodo-benzaldehydes, affords the desired BDPY-porphyrin array in yields of 10-58%. The arrays are soluble in organic solvents and have been characterized by static and time-resolved absorption and fluorescence spectroscopy. The blue-green BDPY absorption complements spectral coverage of the porphyrin chromophores and rivals the intensity of the porphyrin Soret band when eight BDPY accessory pigments are present. Efficient energy transfer from the BDPY pigment(s) to the porphyrin (free base or Zn-chelate) is observed in arrays containing one or two (>90%) or eight (>85%) accessory pigments per porphyrin. Biphasic excited-state decay behavior is exhibited by the BDPY pigments in isolated form and in the arrays. The time constants are ~15 and ~500 ps in the reference compounds (both reflecting deactivation to the ground state) and ~2 and ~20 ps in the arrays (both primarily reflecting energy transfer to the porphyrin). The longer-lived kinetic component comprises ~70% of the decay in each case. Ab initio calculations suggest that the two kinetic components are associated with two energetically accessible excited-state conformers involving the boron-dipyrrin unit and the 5-aryl ring (which is integral to the linker in the arrays). The calculations and experimental results indicate that the two excited-state conformers differ from one another in structure (the planarity of the boron-dipyrrin unit and its orientation with respect to the 5-aryl ring), electronic composition (especially the electron density on the 5-aryl group of the boron-dipyrrin unit), radiative and nonradiative coupling to the ground state, and the rate of energy transfer to the porphyrin constituent in the arrays. The high energy-transfer efficiencies together with favorable light-absorption and chemical properties exhibited by the boron-dipyrrin pigments make them amenable for use in porphyrin-based arrays for molecular photonics applications.

AB - Light-harvesting arrays containing one, two, or eight boron-dipyrrin (BDPY) pigments and one porphyrin (free base or Zn chelate) have been synthesized using a modular building block approach. The reaction of pyrrole and 4-(BDPY)benzaldehyde or 3,5-bis(BDPY)benzaldehyde, prepared by Pd- mediated ethynylation with the corresponding iodo-benzaldehydes, affords the desired BDPY-porphyrin array in yields of 10-58%. The arrays are soluble in organic solvents and have been characterized by static and time-resolved absorption and fluorescence spectroscopy. The blue-green BDPY absorption complements spectral coverage of the porphyrin chromophores and rivals the intensity of the porphyrin Soret band when eight BDPY accessory pigments are present. Efficient energy transfer from the BDPY pigment(s) to the porphyrin (free base or Zn-chelate) is observed in arrays containing one or two (>90%) or eight (>85%) accessory pigments per porphyrin. Biphasic excited-state decay behavior is exhibited by the BDPY pigments in isolated form and in the arrays. The time constants are ~15 and ~500 ps in the reference compounds (both reflecting deactivation to the ground state) and ~2 and ~20 ps in the arrays (both primarily reflecting energy transfer to the porphyrin). The longer-lived kinetic component comprises ~70% of the decay in each case. Ab initio calculations suggest that the two kinetic components are associated with two energetically accessible excited-state conformers involving the boron-dipyrrin unit and the 5-aryl ring (which is integral to the linker in the arrays). The calculations and experimental results indicate that the two excited-state conformers differ from one another in structure (the planarity of the boron-dipyrrin unit and its orientation with respect to the 5-aryl ring), electronic composition (especially the electron density on the 5-aryl group of the boron-dipyrrin unit), radiative and nonradiative coupling to the ground state, and the rate of energy transfer to the porphyrin constituent in the arrays. The high energy-transfer efficiencies together with favorable light-absorption and chemical properties exhibited by the boron-dipyrrin pigments make them amenable for use in porphyrin-based arrays for molecular photonics applications.

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