Photoinduced charge separation in self-assembled cofacial pentamers of zinc-5,10,15,20-tetrakis(perylenediimide)porphyrin

Michael J. Ahrens, Richard F. Kelley, Zachary E X Dance, Michael R. Wasielewski

Research output: Contribution to journalArticle

58 Citations (Scopus)

Abstract

A bichromophoric electron donor-acceptor molecule composed of a zinc tetraphenylporphyrin (ZnTPP) surrounded by four perylene-3,4:9,10- bis(dicarboximide) (PDI) chromophores (ZnTPP-PDI4) was synthesized. The properties of this molecule were compared to a reference molecule having ZnTPP covalently bound to a single PDI (ZnTPP-PDI). In toluene, ZnTPP-PDI 4 self-assembles into monodisperse aggregates of five molecules arranged in a columnar stack, (ZnTPP-PDI4)5. The monodisperse nature of this assembly contrasts sharply with previously reported ZnTPP-PDI4 derivatives having 1,7-bis(3,5-di-t-butylphenoxy) groups (ZnTPP-PPDI4). The size and structure of this assembly in solution was determined by small angle X-ray scattering (SAXS) using a high flux synchrotron X-ray source. The ZnTPP-PDI reference molecule does not aggregate. Femtosecond transient absorption spectroscopy shows that laser excitation of both ZnTPP-PDI and (ZnTPP-PDI4)5 results in quantitative formation of ZnTPP+.-PDI-. radical ion pairs in a few picoseconds. The transient absorption spectra of (ZnTPP-PDI4) 5 suggest that the PDI-. radicals interact strongly with adjacent PDI molecules within the columnar stack. Charge recombination occurs more slowly within (ZnTPP-PDI4)5 (τ = 4.8 ns) than it does in ZnTPP-PDI (τ = 3.0 ns) producing mostly ground state as well as a modest yield of the lowest triplet state of PDI (3*PDI). Formation of 3*PDI occurs by rapid spin-orbit induced intersystem crossing (SO-ISC) directly from the singlet radical ion pair as evidenced by the electron spin polarization pattern exhibited by its time-resolved electron paramagnetic resonance spectrum.

Original languageEnglish
Pages (from-to)1469-1478
Number of pages10
JournalPhysical Chemistry Chemical Physics
Volume9
Issue number12
DOIs
Publication statusPublished - 2007

Fingerprint

Porphyrins
polarization (charge separation)
porphyrins
Zinc
zinc
Molecules
molecules
zinc tetraphenylporphyrin
perylenediimide
assembly
Perylene
Ions
Spin polarization
Laser excitation
Electrons
Toluene
Chromophores
X ray scattering
Synchrotrons
Absorption spectroscopy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Atomic and Molecular Physics, and Optics

Cite this

Photoinduced charge separation in self-assembled cofacial pentamers of zinc-5,10,15,20-tetrakis(perylenediimide)porphyrin. / Ahrens, Michael J.; Kelley, Richard F.; Dance, Zachary E X; Wasielewski, Michael R.

In: Physical Chemistry Chemical Physics, Vol. 9, No. 12, 2007, p. 1469-1478.

Research output: Contribution to journalArticle

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abstract = "A bichromophoric electron donor-acceptor molecule composed of a zinc tetraphenylporphyrin (ZnTPP) surrounded by four perylene-3,4:9,10- bis(dicarboximide) (PDI) chromophores (ZnTPP-PDI4) was synthesized. The properties of this molecule were compared to a reference molecule having ZnTPP covalently bound to a single PDI (ZnTPP-PDI). In toluene, ZnTPP-PDI 4 self-assembles into monodisperse aggregates of five molecules arranged in a columnar stack, (ZnTPP-PDI4)5. The monodisperse nature of this assembly contrasts sharply with previously reported ZnTPP-PDI4 derivatives having 1,7-bis(3,5-di-t-butylphenoxy) groups (ZnTPP-PPDI4). The size and structure of this assembly in solution was determined by small angle X-ray scattering (SAXS) using a high flux synchrotron X-ray source. The ZnTPP-PDI reference molecule does not aggregate. Femtosecond transient absorption spectroscopy shows that laser excitation of both ZnTPP-PDI and (ZnTPP-PDI4)5 results in quantitative formation of ZnTPP+.-PDI-. radical ion pairs in a few picoseconds. The transient absorption spectra of (ZnTPP-PDI4) 5 suggest that the PDI-. radicals interact strongly with adjacent PDI molecules within the columnar stack. Charge recombination occurs more slowly within (ZnTPP-PDI4)5 (τ = 4.8 ns) than it does in ZnTPP-PDI (τ = 3.0 ns) producing mostly ground state as well as a modest yield of the lowest triplet state of PDI (3*PDI). Formation of 3*PDI occurs by rapid spin-orbit induced intersystem crossing (SO-ISC) directly from the singlet radical ion pair as evidenced by the electron spin polarization pattern exhibited by its time-resolved electron paramagnetic resonance spectrum.",
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