Modulation of Radical Ion Pair Lifetimes by the Presence of a Third Spin in Rodlike Donor-Acceptor Triads

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Abstract

It is well known that the molecular structure of an electron donor?acceptor system can be changed to optimize the electronic coupling between photogenerated radical ion pairs (PRPs), resulting in favorable charge separation (CS) and charge recombination (CR) rates. It would be far more convenient to avoid extensive synthetic modifications to the structure to achieve the same ends by perturbing the electronic properties of the PRP. We present here results on PRPs within rodlike donor?acceptor molecules having a covalently attached stable 2,2,6,6-tetramethylpiperidinoxyl radical (T). The distances and orientations between all three radicals are highly restricted by the intervening molecular structure, making it possible to directly measure both the CR dynamics and the spin?spin exchange interaction, 2JPRP, between the radicals within the PRPs. The molecular triads studied are MeOAn?6ANI?PI?T and MeOAn?6ANI?NI?T, where MeOAn = p-methoxyaniline, 6ANI = 4-(N-piperidinyl)naphthalene-1,8-dicarboximide, NI = naphthalene-1,8:4,5-bis(dicarboximide), and PI = pyromellitimide. These molecules have been characterized using femtosecond and nanosecond transient absorption spectroscopy as well as measurements of 2JPRP using magnetic field effects on the triplet state yield resulting from CR. We find that T enhances radical pair intersystem crossing (EISC), resulting in an increase or decrease in the PRP lifetime depending on the relative ordering of the energy levels of the PRP and the local neutral triplet states. This is especially pronounced when the PRP is nearly isoenergetic with the neutral triplet state, as is the case for MeOAn?6ANI?NI?T. The dependence of the 3*NI and 3*6ANI yield on an applied external magnetic field shows a distinct resonance at 2JPRP, the magnitude of which is not perturbed by the presence of the third spin. The sensitivity of this system to changes in spin state may offer ways to externally control the radical ion pair dynamics using pulsed microwaves.

Original languageEnglish
Pages (from-to)2326-2327
Number of pages2
JournalJournal of the American Chemical Society
Volume126
Issue number8
DOIs
Publication statusPublished - Mar 3 2004

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Modulation
Ions
Genetic Recombination
Magnetic Fields
Naphthalene
Molecular Structure
Molecular structure
Magnetic field effects
Molecules
Exchange interactions
Microwaves
Absorption spectroscopy
Electronic properties
Electron energy levels
Spectrum Analysis
Electrons
Magnetic fields

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Modulation of Radical Ion Pair Lifetimes by the Presence of a Third Spin in Rodlike Donor-Acceptor Triads. / Weiss, Emily A; Chernick, Erin T.; Wasielewski, Michael R.

In: Journal of the American Chemical Society, Vol. 126, No. 8, 03.03.2004, p. 2326-2327.

Research output: Contribution to journalArticle

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abstract = "It is well known that the molecular structure of an electron donor?acceptor system can be changed to optimize the electronic coupling between photogenerated radical ion pairs (PRPs), resulting in favorable charge separation (CS) and charge recombination (CR) rates. It would be far more convenient to avoid extensive synthetic modifications to the structure to achieve the same ends by perturbing the electronic properties of the PRP. We present here results on PRPs within rodlike donor?acceptor molecules having a covalently attached stable 2,2,6,6-tetramethylpiperidinoxyl radical (T•). The distances and orientations between all three radicals are highly restricted by the intervening molecular structure, making it possible to directly measure both the CR dynamics and the spin?spin exchange interaction, 2JPRP, between the radicals within the PRPs. The molecular triads studied are MeOAn?6ANI?PI?T• and MeOAn?6ANI?NI?T•, where MeOAn = p-methoxyaniline, 6ANI = 4-(N-piperidinyl)naphthalene-1,8-dicarboximide, NI = naphthalene-1,8:4,5-bis(dicarboximide), and PI = pyromellitimide. These molecules have been characterized using femtosecond and nanosecond transient absorption spectroscopy as well as measurements of 2JPRP using magnetic field effects on the triplet state yield resulting from CR. We find that T• enhances radical pair intersystem crossing (EISC), resulting in an increase or decrease in the PRP lifetime depending on the relative ordering of the energy levels of the PRP and the local neutral triplet states. This is especially pronounced when the PRP is nearly isoenergetic with the neutral triplet state, as is the case for MeOAn?6ANI?NI?T•. The dependence of the 3*NI and 3*6ANI yield on an applied external magnetic field shows a distinct resonance at 2JPRP, the magnitude of which is not perturbed by the presence of the third spin. The sensitivity of this system to changes in spin state may offer ways to externally control the radical ion pair dynamics using pulsed microwaves.",
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