Synthesis, characterization, and photoinduced energy and electron transfer in a supramolecular tetrakis (ruthenium(II) phthalocyanine) perylenediimide pentad

Angel J. Jiménez, Bruno Grimm, Victoria L. Gunderson, Michael T. Vagnini, Sandra Krick Calderon, M. Salomé Rodríguez-Morgade, Michael R Wasielewski, Dirk M. Guldi, Tomás Torres

Research output: Contribution to journalArticle

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Abstract

Metal coordination was probed as a versatile approach for designing a novel electron donor/acceptor hybrid [PDIpy4{Ru(CO)Pc}4] (1), in which four pyridines placed at the bay region of a perylenediimides (PDIpy4) coordinate with four ruthenium phthalocyanine units [Ru(CO)Pc]. This structural motif was expected to promote strong electronic coupling between the electron donors and the electron acceptor, a hypothesis that was confirmed in a full-fledged physicochemical investigation focusing on the ground and excited state reactivities. As far as the ground state is concerned, absorption and electrochemical assays indeed reveal a notable redistribution of electron density, that is, from the electron-donating [Ru(CO)Pc] to the electron-accepting PDIpy4. The most important thing to note in this context is that both the [Ru(CO)Pc] oxidation and the PDIpy4 reduction are rendered more difficult in 1 than in the individual building blocks. Likewise, in the excited state, strong electronic communication is the inception for a rapid charge-transfer process in photoexcited 1. Regardless of exciting [Ru(CO)Pc] or PDIpy4, spectral characteristics of the [RuPc] radical cation (broad absorptive features from 425 to 600 nm with a maximum at 575 nm, as well as a band centered at 725 nm) and of the PDI radical anion (780 nm maximum) emerge. The correspondingly formed radical ion pair state lasts for up to several hundred picoseconds in toluene, for example. On the other hand, employing more polar solvents, such as dichloromethane, destabilizes the radical ion pair state.

Original languageEnglish
Pages (from-to)5024-5032
Number of pages9
JournalChemistry - A European Journal
Volume17
Issue number18
DOIs
Publication statusPublished - Apr 26 2011

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Ruthenium
Carbon Monoxide
Electrons
Excited states
Ground state
Ions
Pyridines
Methylene Chloride
Dichloromethane
Toluene
Pyridine
Anions
Carrier concentration
Cations
Charge transfer
Assays
Negative ions
Positive ions
Metals
phthalocyanine

Keywords

  • charge separation
  • charge transfer
  • perylenediimide
  • phthalocyanines
  • radical ions
  • ruthenium

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Jiménez, A. J., Grimm, B., Gunderson, V. L., Vagnini, M. T., Krick Calderon, S., Rodríguez-Morgade, M. S., ... Torres, T. (2011). Synthesis, characterization, and photoinduced energy and electron transfer in a supramolecular tetrakis (ruthenium(II) phthalocyanine) perylenediimide pentad. Chemistry - A European Journal, 17(18), 5024-5032. https://doi.org/10.1002/chem.201002963

Synthesis, characterization, and photoinduced energy and electron transfer in a supramolecular tetrakis (ruthenium(II) phthalocyanine) perylenediimide pentad. / Jiménez, Angel J.; Grimm, Bruno; Gunderson, Victoria L.; Vagnini, Michael T.; Krick Calderon, Sandra; Rodríguez-Morgade, M. Salomé; Wasielewski, Michael R; Guldi, Dirk M.; Torres, Tomás.

In: Chemistry - A European Journal, Vol. 17, No. 18, 26.04.2011, p. 5024-5032.

Research output: Contribution to journalArticle

Jiménez, Angel J. ; Grimm, Bruno ; Gunderson, Victoria L. ; Vagnini, Michael T. ; Krick Calderon, Sandra ; Rodríguez-Morgade, M. Salomé ; Wasielewski, Michael R ; Guldi, Dirk M. ; Torres, Tomás. / Synthesis, characterization, and photoinduced energy and electron transfer in a supramolecular tetrakis (ruthenium(II) phthalocyanine) perylenediimide pentad. In: Chemistry - A European Journal. 2011 ; Vol. 17, No. 18. pp. 5024-5032.
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