Photoinduced energy and electron transfer reactions in lamellar polyanion/polycation thin films: Toward an inorganic 'leaf'

David M. Kaschak, John T. Lean, Chad C. Waraksa, Geoffrey B. Saupe, Hisanao Usami, Thomas E. Mallouk

Research output: Contribution to journalArticle

240 Citations (Scopus)

Abstract

Sequential adsorption of polyanions and polycations was used to make a five-component energy/electron-transfer cascade, which mimics some of the functions of natural photosynthetic assemblies. The photon antenna part of the system consists of coumarin- and fluorescein-derivatized poly(allylamine hydrochloride) (Coum-PAH and Fl-PAH), palladium(II)tetrakis(4-N,N,N- trimethylanilinium) porphyrin (PdTAPP4+ or palladium(II)tetrakis(4- sulfonatophenyl) porphyrin (PdTSPP4-) layers, interleaved with anionic Zr(HPO4)2 · H2O (α-ZrP) sheets. α-ZrP or HTiNbO5 sheets separate the porphyrin electron donor from a polyviologen electron acceptor layer. Layer- by-layer growth of these thin film assemblies was characterized by atomic force microscopy (AFM) and ellipsometry on planar supports, and by elemental analysis, surface area measurements, and transmission electron microscopy high on surface area silica supports. UV-vis absorption and steady-state emission spectroscopies showed that the overall energy/electron-transfer reaction (Coum → Fl → PdTSPP4- → viologen) occurs with approximate quantum yields of 0.47 and 0.61 for systems containing α-ZrP and HTiNbO5 sheets, respectively. Transient diffuse reflectance spectroscopy established that a porphyrin-viologen charge separated state is formed in the reaction, and that it has an exceptionally long-lived component (τ ≃ 900 μs) with the HTiNbO5 spacer. It is inferred that the semiconducting HTiNbO5 sheets play an active role in relaying the electron from photoexcited PdTSPP4- to the viologen electron acceptor.

Original languageEnglish (US)
Pages (from-to)3435-3445
Number of pages11
JournalJournal of the American Chemical Society
Volume121
Issue number14
DOIs
StatePublished - Apr 14 1999

Fingerprint

Energy Transfer
Viologens
Porphyrins
Electrons
Thin films
Palladium
Polycyclic aromatic hydrocarbons
Spectrum Analysis
Atomic Force Microscopy
Ellipsometry
Emission spectroscopy
Quantum yield
Fluorescein
Transmission Electron Microscopy
Photons
Silicon Dioxide
Adsorption
polycations
polyanions
Atomic force microscopy

All Science Journal Classification (ASJC) codes

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

Cite this

Kaschak, David M. ; Lean, John T. ; Waraksa, Chad C. ; Saupe, Geoffrey B. ; Usami, Hisanao ; Mallouk, Thomas E. / Photoinduced energy and electron transfer reactions in lamellar polyanion/polycation thin films : Toward an inorganic 'leaf'. In: Journal of the American Chemical Society. 1999 ; Vol. 121, No. 14. pp. 3435-3445.
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Photoinduced energy and electron transfer reactions in lamellar polyanion/polycation thin films : Toward an inorganic 'leaf'. / Kaschak, David M.; Lean, John T.; Waraksa, Chad C.; Saupe, Geoffrey B.; Usami, Hisanao; Mallouk, Thomas E.

In: Journal of the American Chemical Society, Vol. 121, No. 14, 14.04.1999, p. 3435-3445.

Research output: Contribution to journalArticle

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T1 - Photoinduced energy and electron transfer reactions in lamellar polyanion/polycation thin films

T2 - Toward an inorganic 'leaf'

AU - Kaschak, David M.

AU - Lean, John T.

AU - Waraksa, Chad C.

AU - Saupe, Geoffrey B.

AU - Usami, Hisanao

AU - Mallouk, Thomas E.

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N2 - Sequential adsorption of polyanions and polycations was used to make a five-component energy/electron-transfer cascade, which mimics some of the functions of natural photosynthetic assemblies. The photon antenna part of the system consists of coumarin- and fluorescein-derivatized poly(allylamine hydrochloride) (Coum-PAH and Fl-PAH), palladium(II)tetrakis(4-N,N,N- trimethylanilinium) porphyrin (PdTAPP4+ or palladium(II)tetrakis(4- sulfonatophenyl) porphyrin (PdTSPP4-) layers, interleaved with anionic Zr(HPO4)2 · H2O (α-ZrP) sheets. α-ZrP or HTiNbO5 sheets separate the porphyrin electron donor from a polyviologen electron acceptor layer. Layer- by-layer growth of these thin film assemblies was characterized by atomic force microscopy (AFM) and ellipsometry on planar supports, and by elemental analysis, surface area measurements, and transmission electron microscopy high on surface area silica supports. UV-vis absorption and steady-state emission spectroscopies showed that the overall energy/electron-transfer reaction (Coum → Fl → PdTSPP4- → viologen) occurs with approximate quantum yields of 0.47 and 0.61 for systems containing α-ZrP and HTiNbO5 sheets, respectively. Transient diffuse reflectance spectroscopy established that a porphyrin-viologen charge separated state is formed in the reaction, and that it has an exceptionally long-lived component (τ ≃ 900 μs) with the HTiNbO5 spacer. It is inferred that the semiconducting HTiNbO5 sheets play an active role in relaying the electron from photoexcited PdTSPP4- to the viologen electron acceptor.

AB - Sequential adsorption of polyanions and polycations was used to make a five-component energy/electron-transfer cascade, which mimics some of the functions of natural photosynthetic assemblies. The photon antenna part of the system consists of coumarin- and fluorescein-derivatized poly(allylamine hydrochloride) (Coum-PAH and Fl-PAH), palladium(II)tetrakis(4-N,N,N- trimethylanilinium) porphyrin (PdTAPP4+ or palladium(II)tetrakis(4- sulfonatophenyl) porphyrin (PdTSPP4-) layers, interleaved with anionic Zr(HPO4)2 · H2O (α-ZrP) sheets. α-ZrP or HTiNbO5 sheets separate the porphyrin electron donor from a polyviologen electron acceptor layer. Layer- by-layer growth of these thin film assemblies was characterized by atomic force microscopy (AFM) and ellipsometry on planar supports, and by elemental analysis, surface area measurements, and transmission electron microscopy high on surface area silica supports. UV-vis absorption and steady-state emission spectroscopies showed that the overall energy/electron-transfer reaction (Coum → Fl → PdTSPP4- → viologen) occurs with approximate quantum yields of 0.47 and 0.61 for systems containing α-ZrP and HTiNbO5 sheets, respectively. Transient diffuse reflectance spectroscopy established that a porphyrin-viologen charge separated state is formed in the reaction, and that it has an exceptionally long-lived component (τ ≃ 900 μs) with the HTiNbO5 spacer. It is inferred that the semiconducting HTiNbO5 sheets play an active role in relaying the electron from photoexcited PdTSPP4- to the viologen electron acceptor.

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