Ultrafast photooxidation of Mn(II)-terpyridine complexes covalently attached to TiO2 nanoparticles

Sabas G. Abuabara; Clyde W. Cady; Jason B. Baxter; Charles A. Schmuttenmaer; Robert H. Crabtree; Gary W. Brudvig; Victor S. Batista

doi:10.1021/jp072380h

Ultrafast photooxidation of Mn(II)-terpyridine complexes covalently attached to TiO₂ nanoparticles

Sabas G. Abuabara, Clyde W. Cady, Jason B. Baxter, Charles A. Schmuttenmaer, Robert H. Crabtree, Gary W. Brudvig, Victor S. Batista

Yale University

Research output: Contribution to journal › Article

74 Citations (Scopus)

Abstract

This paper reports visible-light sensitization of TiO₂ nanoparticles by surface modification with Mn(II)-terpyridine complexes, as evidenced by UV-vis spectroscopy of colloidal thin films and aqueous suspensions. Photoexcitation of the [Mn^II(H₂O) ₃(catechol-terpy)]²⁺/TiO₂ (terpy = 2,2′:6,2″-terpyridine) complex, attached to the TiO₂ surface, leads to interfacial electron transfer within 300 fs as indicated by ultrafast optical pumpterahertz probe transient measurements and computational simulations. Photoinduced interfacial electron transfer is accompanied by Mn(II) → Mn(III) photooxidation. The half-time for regeneration of the Mn(II) complex is ca. 23 s (at 6 K), as monitored by time-resolved measurements of the Mn(II) EPR signal.

Original language	English
Pages (from-to)	11982-11990
Number of pages	9
Journal	Journal of Physical Chemistry C
Volume	111
Issue number	32
DOIs	https://doi.org/10.1021/jp072380h
Publication status	Published - Aug 16 2007

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
Energy(all)
Physical and Theoretical Chemistry
Surfaces, Coatings and Films

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10.1021/jp072380h

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Abuabara, S. G., Cady, C. W., Baxter, J. B., Schmuttenmaer, C. A., Crabtree, R. H., Brudvig, G. W., & Batista, V. S. (2007). Ultrafast photooxidation of Mn(II)-terpyridine complexes covalently attached to TiO₂ nanoparticles. Journal of Physical Chemistry C, 111(32), 11982-11990. https://doi.org/10.1021/jp072380h

Ultrafast photooxidation of Mn(II)-terpyridine complexes covalently attached to TiO₂ nanoparticles. / Abuabara, Sabas G.; Cady, Clyde W.; Baxter, Jason B.; Schmuttenmaer, Charles A.; Crabtree, Robert H.; Brudvig, Gary W.; Batista, Victor S.

In: Journal of Physical Chemistry C, Vol. 111, No. 32, 16.08.2007, p. 11982-11990.

Research output: Contribution to journal › Article

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title = "Ultrafast photooxidation of Mn(II)-terpyridine complexes covalently attached to TiO2 nanoparticles",

abstract = "This paper reports visible-light sensitization of TiO2 nanoparticles by surface modification with Mn(II)-terpyridine complexes, as evidenced by UV-vis spectroscopy of colloidal thin films and aqueous suspensions. Photoexcitation of the [MnII(H2O) 3(catechol-terpy)]2+/TiO2 (terpy = 2,2′:6,2″-terpyridine) complex, attached to the TiO2 surface, leads to interfacial electron transfer within 300 fs as indicated by ultrafast optical pumpterahertz probe transient measurements and computational simulations. Photoinduced interfacial electron transfer is accompanied by Mn(II) → Mn(III) photooxidation. The half-time for regeneration of the Mn(II) complex is ca. 23 s (at 6 K), as monitored by time-resolved measurements of the Mn(II) EPR signal.",

author = "Abuabara, {Sabas G.} and Cady, {Clyde W.} and Baxter, {Jason B.} and Schmuttenmaer, {Charles A.} and Crabtree, {Robert H.} and Brudvig, {Gary W.} and Batista, {Victor S.}",

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AU - Abuabara, Sabas G.

AU - Cady, Clyde W.

AU - Baxter, Jason B.

AU - Schmuttenmaer, Charles A.

AU - Crabtree, Robert H.

AU - Brudvig, Gary W.

AU - Batista, Victor S.

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N2 - This paper reports visible-light sensitization of TiO2 nanoparticles by surface modification with Mn(II)-terpyridine complexes, as evidenced by UV-vis spectroscopy of colloidal thin films and aqueous suspensions. Photoexcitation of the [MnII(H2O) 3(catechol-terpy)]2+/TiO2 (terpy = 2,2′:6,2″-terpyridine) complex, attached to the TiO2 surface, leads to interfacial electron transfer within 300 fs as indicated by ultrafast optical pumpterahertz probe transient measurements and computational simulations. Photoinduced interfacial electron transfer is accompanied by Mn(II) → Mn(III) photooxidation. The half-time for regeneration of the Mn(II) complex is ca. 23 s (at 6 K), as monitored by time-resolved measurements of the Mn(II) EPR signal.

AB - This paper reports visible-light sensitization of TiO2 nanoparticles by surface modification with Mn(II)-terpyridine complexes, as evidenced by UV-vis spectroscopy of colloidal thin films and aqueous suspensions. Photoexcitation of the [MnII(H2O) 3(catechol-terpy)]2+/TiO2 (terpy = 2,2′:6,2″-terpyridine) complex, attached to the TiO2 surface, leads to interfacial electron transfer within 300 fs as indicated by ultrafast optical pumpterahertz probe transient measurements and computational simulations. Photoinduced interfacial electron transfer is accompanied by Mn(II) → Mn(III) photooxidation. The half-time for regeneration of the Mn(II) complex is ca. 23 s (at 6 K), as monitored by time-resolved measurements of the Mn(II) EPR signal.

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