Single crystal electron paramagnetic resonance spectra of triplet excitons in [(Cp*Ru)2(η6,η6-[2 2](1,4)cyclophane)2+][(TCNQ)42-]

John R. Morton; Keith F. Preston; Michael D. Ward; Paul J. Fagan

doi:10.1063/1.456009

Single crystal electron paramagnetic resonance spectra of triplet excitons in [(Cp*Ru)₂(η⁶,η⁶-[2 ₂](1,4)cyclophane)²⁺][(TCNQ)₄^2-]

John R. Morton, Keith F. Preston, Michael D. Ward, Paul J. Fagan

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Single crystals of [(Cp*Ru)₂(η⁶, η⁶-[2₂](1,4)cyclophane)²⁺][(TCNQ) ₄^2-] (Cp* = η⁵-C₅Me ₅, TCNQ = tetracyanoquinodimethane) have been examined by EPR spectroscopy at temperatures down to 4 K. The anisotropic spectrum measured in the 77-150 K range is characteristic of an excitonic triplet species (I). This behavior is attributed to interactions between electrons located in one of the TCNQ acceptor stacks present in the title compound. The direction of maximum electronic interaction coincides with the stacking axis of the crystals (the crystallographic a axis). Intensity measurements establish that I is a thermally excited triplet with a J = 560 ± 30 cm^-1, exhibiting zero field splittings of \D\ = 187 MHz (66G) and \E\ = 32 MHz (10 G). A second although weaker feature in the spectrum is tentatively assigned to a second triplet (species II) having very much smaller values of \D| and J than those of I. Species II is attributed to an impurity present in very low concentrations.

Original language	English (US)
Pages (from-to)	2148-2153
Number of pages	6
Journal	The Journal of Chemical Physics
Volume	90
Issue number	4
DOIs	https://doi.org/10.1063/1.456009
State	Published - 1989

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General Physics and Astronomy
Physical and Theoretical Chemistry

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title = "Single crystal electron paramagnetic resonance spectra of triplet excitons in [(Cp*Ru)2(η6,η6-[2 2](1,4)cyclophane)2+][(TCNQ)42-]",

abstract = "Single crystals of [(Cp*Ru)2(η6, η6-[22](1,4)cyclophane)2+][(TCNQ) 42-] (Cp* = η5-C5Me 5, TCNQ = tetracyanoquinodimethane) have been examined by EPR spectroscopy at temperatures down to 4 K. The anisotropic spectrum measured in the 77-150 K range is characteristic of an excitonic triplet species (I). This behavior is attributed to interactions between electrons located in one of the TCNQ acceptor stacks present in the title compound. The direction of maximum electronic interaction coincides with the stacking axis of the crystals (the crystallographic a axis). Intensity measurements establish that I is a thermally excited triplet with a J = 560 ± 30 cm-1, exhibiting zero field splittings of \D\ = 187 MHz (66G) and \E\ = 32 MHz (10 G). A second although weaker feature in the spectrum is tentatively assigned to a second triplet (species II) having very much smaller values of \D| and J than those of I. Species II is attributed to an impurity present in very low concentrations.",

author = "Morton, {John R.} and Preston, {Keith F.} and Ward, {Michael D.} and Fagan, {Paul J.}",

year = "1989",

doi = "10.1063/1.456009",

language = "English (US)",

volume = "90",

pages = "2148--2153",

journal = "The Journal of Chemical Physics",

issn = "0021-9606",

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T1 - Single crystal electron paramagnetic resonance spectra of triplet excitons in [(Cp*Ru)2(η6,η6-[2 2](1,4)cyclophane)2+][(TCNQ)42-]

AU - Morton, John R.

AU - Preston, Keith F.

AU - Ward, Michael D.

AU - Fagan, Paul J.

PY - 1989

Y1 - 1989

N2 - Single crystals of [(Cp*Ru)2(η6, η6-[22](1,4)cyclophane)2+][(TCNQ) 42-] (Cp* = η5-C5Me 5, TCNQ = tetracyanoquinodimethane) have been examined by EPR spectroscopy at temperatures down to 4 K. The anisotropic spectrum measured in the 77-150 K range is characteristic of an excitonic triplet species (I). This behavior is attributed to interactions between electrons located in one of the TCNQ acceptor stacks present in the title compound. The direction of maximum electronic interaction coincides with the stacking axis of the crystals (the crystallographic a axis). Intensity measurements establish that I is a thermally excited triplet with a J = 560 ± 30 cm-1, exhibiting zero field splittings of \D\ = 187 MHz (66G) and \E\ = 32 MHz (10 G). A second although weaker feature in the spectrum is tentatively assigned to a second triplet (species II) having very much smaller values of \D| and J than those of I. Species II is attributed to an impurity present in very low concentrations.

AB - Single crystals of [(Cp*Ru)2(η6, η6-[22](1,4)cyclophane)2+][(TCNQ) 42-] (Cp* = η5-C5Me 5, TCNQ = tetracyanoquinodimethane) have been examined by EPR spectroscopy at temperatures down to 4 K. The anisotropic spectrum measured in the 77-150 K range is characteristic of an excitonic triplet species (I). This behavior is attributed to interactions between electrons located in one of the TCNQ acceptor stacks present in the title compound. The direction of maximum electronic interaction coincides with the stacking axis of the crystals (the crystallographic a axis). Intensity measurements establish that I is a thermally excited triplet with a J = 560 ± 30 cm-1, exhibiting zero field splittings of \D\ = 187 MHz (66G) and \E\ = 32 MHz (10 G). A second although weaker feature in the spectrum is tentatively assigned to a second triplet (species II) having very much smaller values of \D| and J than those of I. Species II is attributed to an impurity present in very low concentrations.

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Single crystal electron paramagnetic resonance spectra of triplet excitons in [(Cp*Ru)₂(η⁶,η⁶-[2 ₂](1,4)cyclophane)²⁺][(TCNQ)₄^2-]

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