Single-crystal electron paramagnetic resonance study of triplet excitons in [Fe(mesitylene)22+] [C3(C(CN) 2)3-]2

J. R. Morton; K. F. Preston; Y. Le Page; A. J. Williams; M. D. Ward

doi:10.1063/1.459055

Single-crystal electron paramagnetic resonance study of triplet excitons in [Fe(mesitylene)₂²⁺] [C₃(C(CN) ₂)₃^-]₂

J. R. Morton, K. F. Preston, Y. Le Page, A. J. Williams, M. D. Ward

Chemistry

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

Abstract

Single crystals of [Fe(mesitylene)₂²⁺] [C ₃(C(CN)₂)₃^-]₂ exhibit an intense EPR spectrum with anisotropy and fine structure typical of an electronic triplet species (S=1). From measurements of the fine-structure splitting as a function of angle in three orthogonal crystal planes, it has been established that the spin-spin interaction tensor is nearly axial, D = (-218, 116, 105 MHz), and that the g tensor is almost isotropic with g_iso = 2.0027. The zero-field splitting parameters were determined as |D| = 327.8 MHz (117 G) and |E| = 5.7 MHz (2 G). Comparison of the principal directions of D with vectors within the known crystal structure shows that the triplet comprises a radical pair formed between nearest neighboring anions. The principal values and directions of D for the biradical compare well with those calculated for the unpaired spin density distribution deduced for the monoradical from its isotropic spectrum and from INDO calculations.

Original language	English (US)
Pages (from-to)	2222-2227
Number of pages	6
Journal	The Journal of Chemical Physics
Volume	93
Issue number	4
DOIs	https://doi.org/10.1063/1.459055
State	Published - 1990

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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title = "Single-crystal electron paramagnetic resonance study of triplet excitons in [Fe(mesitylene)22+] [C3(C(CN) 2)3-]2",

abstract = "Single crystals of [Fe(mesitylene)22+] [C 3(C(CN)2)3-]2 exhibit an intense EPR spectrum with anisotropy and fine structure typical of an electronic triplet species (S=1). From measurements of the fine-structure splitting as a function of angle in three orthogonal crystal planes, it has been established that the spin-spin interaction tensor is nearly axial, D = (-218, 116, 105 MHz), and that the g tensor is almost isotropic with giso = 2.0027. The zero-field splitting parameters were determined as |D| = 327.8 MHz (117 G) and |E| = 5.7 MHz (2 G). Comparison of the principal directions of D with vectors within the known crystal structure shows that the triplet comprises a radical pair formed between nearest neighboring anions. The principal values and directions of D for the biradical compare well with those calculated for the unpaired spin density distribution deduced for the monoradical from its isotropic spectrum and from INDO calculations.",

author = "Morton, {J. R.} and Preston, {K. F.} and {Le Page}, Y. and Williams, {A. J.} and Ward, {M. D.}",

year = "1990",

doi = "10.1063/1.459055",

language = "English (US)",

volume = "93",

pages = "2222--2227",

journal = "The Journal of Chemical Physics",

issn = "0021-9606",

publisher = "American Institute of Physics",

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TY - JOUR

T1 - Single-crystal electron paramagnetic resonance study of triplet excitons in [Fe(mesitylene)22+] [C3(C(CN) 2)3-]2

AU - Morton, J. R.

AU - Preston, K. F.

AU - Le Page, Y.

AU - Williams, A. J.

AU - Ward, M. D.

PY - 1990

Y1 - 1990

N2 - Single crystals of [Fe(mesitylene)22+] [C 3(C(CN)2)3-]2 exhibit an intense EPR spectrum with anisotropy and fine structure typical of an electronic triplet species (S=1). From measurements of the fine-structure splitting as a function of angle in three orthogonal crystal planes, it has been established that the spin-spin interaction tensor is nearly axial, D = (-218, 116, 105 MHz), and that the g tensor is almost isotropic with giso = 2.0027. The zero-field splitting parameters were determined as |D| = 327.8 MHz (117 G) and |E| = 5.7 MHz (2 G). Comparison of the principal directions of D with vectors within the known crystal structure shows that the triplet comprises a radical pair formed between nearest neighboring anions. The principal values and directions of D for the biradical compare well with those calculated for the unpaired spin density distribution deduced for the monoradical from its isotropic spectrum and from INDO calculations.

AB - Single crystals of [Fe(mesitylene)22+] [C 3(C(CN)2)3-]2 exhibit an intense EPR spectrum with anisotropy and fine structure typical of an electronic triplet species (S=1). From measurements of the fine-structure splitting as a function of angle in three orthogonal crystal planes, it has been established that the spin-spin interaction tensor is nearly axial, D = (-218, 116, 105 MHz), and that the g tensor is almost isotropic with giso = 2.0027. The zero-field splitting parameters were determined as |D| = 327.8 MHz (117 G) and |E| = 5.7 MHz (2 G). Comparison of the principal directions of D with vectors within the known crystal structure shows that the triplet comprises a radical pair formed between nearest neighboring anions. The principal values and directions of D for the biradical compare well with those calculated for the unpaired spin density distribution deduced for the monoradical from its isotropic spectrum and from INDO calculations.

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JF - The Journal of Chemical Physics

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ER -

Single-crystal electron paramagnetic resonance study of triplet excitons in [Fe(mesitylene)₂²⁺] [C₃(C(CN) ₂)₃^-]₂

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