Long-range electron transfer in porphyrin-containing [2]-rotaxanes: Tuning the rate by metal cation coordination

Mikael Andersson, Myriam Linke, Jean Claude Chambron, Jan Davidsson, Valérie Heitz, Leif Hammarström, Jean Pierre Sauvage

Research output: Contribution to journalArticle

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Abstract

A series of [2]-rotaxanes has been synthesized in which two Zn(II)-porphyrins (ZnP) electron donors were attached as stoppers on the rod. A macrocycle attached to a Au(III)-porphyrin (AuP+) acceptor was threaded on the rod. By selective excitation of either porphyrin, we could induce an electron transfer from the ZnP to the AuP+ unit that generated the same ZnP.+-AuP. charge-transfer state irrespective of which porphyrin was excited. Although the reactants were linked only by mechanical or coordination bonds, electron-transfer rate constants up to 1.2 × 1010 s-1 were obtained over a 15-17 Å edge-to-edge distance between the porphyrins. The resulting charge-transfer state had a relatively long lifetime of 10-40 ns and was formed in high yield (>80%) in most cases. By a simple variation of the link between the reactants, viz. a coordination of the phenanthroline units on the rotaxane rod and ring by either Ag+ or Cu+, we could enhance the electron-transfer rate from the ZnP to the excited 3AuP+. We interpret our data in terms of an enhanced super-exchange mechanism with Ag+ and a change to a stepwise hopping mechanism with Cu+, involving the oxidized Cu(phen)2 2+ unit as a real intermediate. When the ZnP unit was excited instead, electron transfer from the excited 1ZnP to AuP+ was not affected, or even slowed, by Ag+ or Cu+. We discuss this asymmetry in terms of the different orbitals involved in mediating the reaction in an electron-and a hole-transfer mechanism. Our results show the possibility to tune the rates of electron transfer between noncovalently linked reactants by a convenient modification of the link. The different effect of Ag+ and Cu+ on the rate with ZnP and AuP+ excitation shows an additional possibility to control the electron-transfer reactions by selective excitation. We also found that coordination of the Cu+ introduced an energy-transfer reaction from 1ZnP to Cu(phen)2 + (k = 5.1 × 109 s-1) that proceeded in competition with electron transfer to AuP+ and was followed by a quantitative energy transfer to give the 3ZnP state (k = 1.5 × 109 s-1).

Original languageEnglish
Pages (from-to)4347-4362
Number of pages16
JournalJournal of the American Chemical Society
Volume124
Issue number16
DOIs
Publication statusPublished - Apr 24 2002

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Rotaxanes
Porphyrins
Cations
Tuning
Positive ions
Metals
Electrons
Energy Transfer
Energy transfer
Charge transfer
Phenanthrolines
Rate constants

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Long-range electron transfer in porphyrin-containing [2]-rotaxanes : Tuning the rate by metal cation coordination. / Andersson, Mikael; Linke, Myriam; Chambron, Jean Claude; Davidsson, Jan; Heitz, Valérie; Hammarström, Leif; Sauvage, Jean Pierre.

In: Journal of the American Chemical Society, Vol. 124, No. 16, 24.04.2002, p. 4347-4362.

Research output: Contribution to journalArticle

Andersson, Mikael ; Linke, Myriam ; Chambron, Jean Claude ; Davidsson, Jan ; Heitz, Valérie ; Hammarström, Leif ; Sauvage, Jean Pierre. / Long-range electron transfer in porphyrin-containing [2]-rotaxanes : Tuning the rate by metal cation coordination. In: Journal of the American Chemical Society. 2002 ; Vol. 124, No. 16. pp. 4347-4362.
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AU - Heitz, Valérie

AU - Hammarström, Leif

AU - Sauvage, Jean Pierre

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N2 - A series of [2]-rotaxanes has been synthesized in which two Zn(II)-porphyrins (ZnP) electron donors were attached as stoppers on the rod. A macrocycle attached to a Au(III)-porphyrin (AuP+) acceptor was threaded on the rod. By selective excitation of either porphyrin, we could induce an electron transfer from the ZnP to the AuP+ unit that generated the same ZnP.+-AuP. charge-transfer state irrespective of which porphyrin was excited. Although the reactants were linked only by mechanical or coordination bonds, electron-transfer rate constants up to 1.2 × 1010 s-1 were obtained over a 15-17 Å edge-to-edge distance between the porphyrins. The resulting charge-transfer state had a relatively long lifetime of 10-40 ns and was formed in high yield (>80%) in most cases. By a simple variation of the link between the reactants, viz. a coordination of the phenanthroline units on the rotaxane rod and ring by either Ag+ or Cu+, we could enhance the electron-transfer rate from the ZnP to the excited 3AuP+. We interpret our data in terms of an enhanced super-exchange mechanism with Ag+ and a change to a stepwise hopping mechanism with Cu+, involving the oxidized Cu(phen)2 2+ unit as a real intermediate. When the ZnP unit was excited instead, electron transfer from the excited 1ZnP to AuP+ was not affected, or even slowed, by Ag+ or Cu+. We discuss this asymmetry in terms of the different orbitals involved in mediating the reaction in an electron-and a hole-transfer mechanism. Our results show the possibility to tune the rates of electron transfer between noncovalently linked reactants by a convenient modification of the link. The different effect of Ag+ and Cu+ on the rate with ZnP and AuP+ excitation shows an additional possibility to control the electron-transfer reactions by selective excitation. We also found that coordination of the Cu+ introduced an energy-transfer reaction from 1ZnP to Cu(phen)2 + (k = 5.1 × 109 s-1) that proceeded in competition with electron transfer to AuP+ and was followed by a quantitative energy transfer to give the 3ZnP state (k = 1.5 × 109 s-1).

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