Hexaazaoctadecahydrocoronene. Structural and physical properties of [HOC]n (n=0, 1+, 2+, 3+, 4+)

Joel S. Miller, Dravid A. Dixon, Joseph C. Calabrese, Carlos Vazquez, Paul J. Krusic, Michael Ward, E. Wasserman, Richard L. Harlow

Research output: Contribution to journalArticle

Abstract

Hexaazaoctadecahydrocoronene and its mono-, di-, tri-, and tetracations, [HOC]n (n = 0, 1+, 2+, 3+, 4+), have been prepared and characterized by X-ray diffraction, EPR, magnetic susceptibility, and electronic and vibrational spectroscopies. HOC, [HOC]+[BF4],- [HOC]+[TCNE]- (TCNE = tetracyanoethylene), [HOC]+[F3CSO3]-, [HOC]2+{[PF6]-}2, [HOC]2+{[BF4]-}2, [HOC]2+{[C(CN)3]-}2, [HOC]2+{C[C(CN)2]3}2-, [HOC]2+{Ni[S2C2(CF3) 2]22-}2, [HOC]3+{[PF6]-}3, [HOC]3+{[SbF6]-}3, and [HOC]4+{[SbF6]- 4·MeCN have been by studied by single-crystal X-ray diffraction. HOC and [HOC]4+ have essentially equivalent C6-ring C-C bond distances averaging 1.397 and 1.436 Å, respectively. Their average C6-ring C-N distances are 1.416 and 1.318 Å, respectively. The dication, [HOC]2+, has a distorted (Jahn-Teller) structure corresponding to coupled cyanine fragments with distinctly different short (1.395-Å) and long (1.471-Å) C6-ring C-C and C-N (1.337- and 1.405-Å) distances. The 1+ and 3+ radical ions also show distorted structures, although the distortions are smaller than observed for the 2+ structure. The short C6-ring C-C bond distances are 1.382 and 1.417 Å, and the long C6-ring C-C bond distances are 1.444 and 1.439 Å, while the short C6-ring C-N bond distances are 1.371 and 1.326 Å and the long C6-ring C-N bond distances are 1.422 and 1.339 Å, respectively. Solid-state magnetic susceptibility measurements show that the n = 0, 2+, and 4+ compounds are diamagnetic and that the n= 1+ 3+ salts are S = 1/2 paramagnets that obey the Curie-Weiss expression between 2 and 320 K. The effective moments, μeff, and Curie-Weiss constants, are 1.77 and 1.75 μB and θ = -3.3 and -0.9 K for the mono- and trications, respectively. The n = 1+ and 3+ radical cations are fluxional in solution. The EPR spectrum of [HOC]+ in the fast-exchange limit (25°C) shows that all protons N's have the same hyperfine splitting (2.56 G, g = 2.003 15). In the slow-exchange limit (-90°C), arc 2 of 12 equivalent protons (0.974 and 4.222 G) and 6 equivaleat N's (2.595 G). This precludes the observation of a Jahn-Teller distortion in solution. The [HOC]3+ ion is fluxional in solution as it exhibits fast-exchange behavior at -60°C [a(24H) = a(6 N) = 2.81 G; g = 2.0310]. EPR of polycrystalline [HOC]2+ salts show the presence of thermally accessible triplet species whose zero-field splitting parameters are |D| = 0.0550 ±0.0008 cm-1 and |E| = 0.0024 = ±0.0005 cm-1 and are appropriate for triplet states of less than 3-fold symmetry. The temperature of the ΔM = ± 2EPR absorption afforded the seperation between the ground singlet state and the excited triplet state of the dictation for a variety of [HOC]2+ salts. For most counternions, these separations are greater than 3 kcal/mol (1050 cm-1, 0.13 eV), Solid-state magnetic susceptibility measurements for [HOC]2+ with singlet-triplet gaps less 4.0 kcal/mol show in susceptibilities athigher temperatures, consistent with the presence of thermally populated triplet excited states. Magnetic susceptibility amd single-crystal X-ray structures of the dication in the crystalline materials of this study are consistent with a singlet ground state. Molecular orbital (ab initio) calculations are in general agreement with the above results.

Original languageEnglish (US)
Pages (from-to)381-398
Number of pages18
JournalJournal of the American Chemical Society
Volume112
Issue number1
StatePublished - 1990

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Magnetic susceptibility
Structural properties
Physical properties
Salts
Paramagnetic resonance
X-Ray Diffraction
Protons
Excited states
Ions
Ground state
Ion exchange
Temperature
Single crystals
Jahn-Teller effect
X ray diffraction
Vibrational spectroscopy
Cations
Spectrum Analysis
Molecular orbitals
Observation

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Miller, J. S., Dixon, D. A., Calabrese, J. C., Vazquez, C., Krusic, P. J., Ward, M., ... Harlow, R. L. (1990). Hexaazaoctadecahydrocoronene. Structural and physical properties of [HOC]n (n=0, 1+, 2+, 3+, 4+). Journal of the American Chemical Society, 112(1), 381-398.

Hexaazaoctadecahydrocoronene. Structural and physical properties of [HOC]n (n=0, 1+, 2+, 3+, 4+). / Miller, Joel S.; Dixon, Dravid A.; Calabrese, Joseph C.; Vazquez, Carlos; Krusic, Paul J.; Ward, Michael; Wasserman, E.; Harlow, Richard L.

In: Journal of the American Chemical Society, Vol. 112, No. 1, 1990, p. 381-398.

Research output: Contribution to journalArticle

Miller, JS, Dixon, DA, Calabrese, JC, Vazquez, C, Krusic, PJ, Ward, M, Wasserman, E & Harlow, RL 1990, 'Hexaazaoctadecahydrocoronene. Structural and physical properties of [HOC]n (n=0, 1+, 2+, 3+, 4+)', Journal of the American Chemical Society, vol. 112, no. 1, pp. 381-398.
Miller, Joel S. ; Dixon, Dravid A. ; Calabrese, Joseph C. ; Vazquez, Carlos ; Krusic, Paul J. ; Ward, Michael ; Wasserman, E. ; Harlow, Richard L. / Hexaazaoctadecahydrocoronene. Structural and physical properties of [HOC]n (n=0, 1+, 2+, 3+, 4+). In: Journal of the American Chemical Society. 1990 ; Vol. 112, No. 1. pp. 381-398.
@article{74af1bcbaf634d72bf9fe6c5a4d17b62,
title = "Hexaazaoctadecahydrocoronene. Structural and physical properties of [HOC]n (n=0, 1+, 2+, 3+, 4+)",
abstract = "Hexaazaoctadecahydrocoronene and its mono-, di-, tri-, and tetracations, [HOC]n (n = 0, 1+, 2+, 3+, 4+), have been prepared and characterized by X-ray diffraction, EPR, magnetic susceptibility, and electronic and vibrational spectroscopies. HOC, [HOC]+[BF4],- [HOC]+[TCNE]- (TCNE = tetracyanoethylene), [HOC]+[F3CSO3]-, [HOC]2+{[PF6]-}2, [HOC]2+{[BF4]-}2, [HOC]2+{[C(CN)3]-}2, [HOC]2+{C[C(CN)2]3}2-, [HOC]2+{Ni[S2C2(CF3) 2]22-}2, [HOC]3+{[PF6]-}3, [HOC]3+{[SbF6]-}3, and [HOC]4+{[SbF6]- 4·MeCN have been by studied by single-crystal X-ray diffraction. HOC and [HOC]4+ have essentially equivalent C6-ring C-C bond distances averaging 1.397 and 1.436 {\AA}, respectively. Their average C6-ring C-N distances are 1.416 and 1.318 {\AA}, respectively. The dication, [HOC]2+, has a distorted (Jahn-Teller) structure corresponding to coupled cyanine fragments with distinctly different short (1.395-{\AA}) and long (1.471-{\AA}) C6-ring C-C and C-N (1.337- and 1.405-{\AA}) distances. The 1+ and 3+ radical ions also show distorted structures, although the distortions are smaller than observed for the 2+ structure. The short C6-ring C-C bond distances are 1.382 and 1.417 {\AA}, and the long C6-ring C-C bond distances are 1.444 and 1.439 {\AA}, while the short C6-ring C-N bond distances are 1.371 and 1.326 {\AA} and the long C6-ring C-N bond distances are 1.422 and 1.339 {\AA}, respectively. Solid-state magnetic susceptibility measurements show that the n = 0, 2+, and 4+ compounds are diamagnetic and that the n= 1+ 3+ salts are S = 1/2 paramagnets that obey the Curie-Weiss expression between 2 and 320 K. The effective moments, μeff, and Curie-Weiss constants, are 1.77 and 1.75 μB and θ = -3.3 and -0.9 K for the mono- and trications, respectively. The n = 1+ and 3+ radical cations are fluxional in solution. The EPR spectrum of [HOC]+ in the fast-exchange limit (25°C) shows that all protons N's have the same hyperfine splitting (2.56 G, g = 2.003 15). In the slow-exchange limit (-90°C), arc 2 of 12 equivalent protons (0.974 and 4.222 G) and 6 equivaleat N's (2.595 G). This precludes the observation of a Jahn-Teller distortion in solution. The [HOC]3+ ion is fluxional in solution as it exhibits fast-exchange behavior at -60°C [a(24H) = a(6 N) = 2.81 G; g = 2.0310]. EPR of polycrystalline [HOC]2+ salts show the presence of thermally accessible triplet species whose zero-field splitting parameters are |D| = 0.0550 ±0.0008 cm-1 and |E| = 0.0024 = ±0.0005 cm-1 and are appropriate for triplet states of less than 3-fold symmetry. The temperature of the ΔM = ± 2EPR absorption afforded the seperation between the ground singlet state and the excited triplet state of the dictation for a variety of [HOC]2+ salts. For most counternions, these separations are greater than 3 kcal/mol (1050 cm-1, 0.13 eV), Solid-state magnetic susceptibility measurements for [HOC]2+ with singlet-triplet gaps less 4.0 kcal/mol show in susceptibilities athigher temperatures, consistent with the presence of thermally populated triplet excited states. Magnetic susceptibility amd single-crystal X-ray structures of the dication in the crystalline materials of this study are consistent with a singlet ground state. Molecular orbital (ab initio) calculations are in general agreement with the above results.",
author = "Miller, {Joel S.} and Dixon, {Dravid A.} and Calabrese, {Joseph C.} and Carlos Vazquez and Krusic, {Paul J.} and Michael Ward and E. Wasserman and Harlow, {Richard L.}",
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language = "English (US)",
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pages = "381--398",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
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TY - JOUR

T1 - Hexaazaoctadecahydrocoronene. Structural and physical properties of [HOC]n (n=0, 1+, 2+, 3+, 4+)

AU - Miller, Joel S.

AU - Dixon, Dravid A.

AU - Calabrese, Joseph C.

AU - Vazquez, Carlos

AU - Krusic, Paul J.

AU - Ward, Michael

AU - Wasserman, E.

AU - Harlow, Richard L.

PY - 1990

Y1 - 1990

N2 - Hexaazaoctadecahydrocoronene and its mono-, di-, tri-, and tetracations, [HOC]n (n = 0, 1+, 2+, 3+, 4+), have been prepared and characterized by X-ray diffraction, EPR, magnetic susceptibility, and electronic and vibrational spectroscopies. HOC, [HOC]+[BF4],- [HOC]+[TCNE]- (TCNE = tetracyanoethylene), [HOC]+[F3CSO3]-, [HOC]2+{[PF6]-}2, [HOC]2+{[BF4]-}2, [HOC]2+{[C(CN)3]-}2, [HOC]2+{C[C(CN)2]3}2-, [HOC]2+{Ni[S2C2(CF3) 2]22-}2, [HOC]3+{[PF6]-}3, [HOC]3+{[SbF6]-}3, and [HOC]4+{[SbF6]- 4·MeCN have been by studied by single-crystal X-ray diffraction. HOC and [HOC]4+ have essentially equivalent C6-ring C-C bond distances averaging 1.397 and 1.436 Å, respectively. Their average C6-ring C-N distances are 1.416 and 1.318 Å, respectively. The dication, [HOC]2+, has a distorted (Jahn-Teller) structure corresponding to coupled cyanine fragments with distinctly different short (1.395-Å) and long (1.471-Å) C6-ring C-C and C-N (1.337- and 1.405-Å) distances. The 1+ and 3+ radical ions also show distorted structures, although the distortions are smaller than observed for the 2+ structure. The short C6-ring C-C bond distances are 1.382 and 1.417 Å, and the long C6-ring C-C bond distances are 1.444 and 1.439 Å, while the short C6-ring C-N bond distances are 1.371 and 1.326 Å and the long C6-ring C-N bond distances are 1.422 and 1.339 Å, respectively. Solid-state magnetic susceptibility measurements show that the n = 0, 2+, and 4+ compounds are diamagnetic and that the n= 1+ 3+ salts are S = 1/2 paramagnets that obey the Curie-Weiss expression between 2 and 320 K. The effective moments, μeff, and Curie-Weiss constants, are 1.77 and 1.75 μB and θ = -3.3 and -0.9 K for the mono- and trications, respectively. The n = 1+ and 3+ radical cations are fluxional in solution. The EPR spectrum of [HOC]+ in the fast-exchange limit (25°C) shows that all protons N's have the same hyperfine splitting (2.56 G, g = 2.003 15). In the slow-exchange limit (-90°C), arc 2 of 12 equivalent protons (0.974 and 4.222 G) and 6 equivaleat N's (2.595 G). This precludes the observation of a Jahn-Teller distortion in solution. The [HOC]3+ ion is fluxional in solution as it exhibits fast-exchange behavior at -60°C [a(24H) = a(6 N) = 2.81 G; g = 2.0310]. EPR of polycrystalline [HOC]2+ salts show the presence of thermally accessible triplet species whose zero-field splitting parameters are |D| = 0.0550 ±0.0008 cm-1 and |E| = 0.0024 = ±0.0005 cm-1 and are appropriate for triplet states of less than 3-fold symmetry. The temperature of the ΔM = ± 2EPR absorption afforded the seperation between the ground singlet state and the excited triplet state of the dictation for a variety of [HOC]2+ salts. For most counternions, these separations are greater than 3 kcal/mol (1050 cm-1, 0.13 eV), Solid-state magnetic susceptibility measurements for [HOC]2+ with singlet-triplet gaps less 4.0 kcal/mol show in susceptibilities athigher temperatures, consistent with the presence of thermally populated triplet excited states. Magnetic susceptibility amd single-crystal X-ray structures of the dication in the crystalline materials of this study are consistent with a singlet ground state. Molecular orbital (ab initio) calculations are in general agreement with the above results.

AB - Hexaazaoctadecahydrocoronene and its mono-, di-, tri-, and tetracations, [HOC]n (n = 0, 1+, 2+, 3+, 4+), have been prepared and characterized by X-ray diffraction, EPR, magnetic susceptibility, and electronic and vibrational spectroscopies. HOC, [HOC]+[BF4],- [HOC]+[TCNE]- (TCNE = tetracyanoethylene), [HOC]+[F3CSO3]-, [HOC]2+{[PF6]-}2, [HOC]2+{[BF4]-}2, [HOC]2+{[C(CN)3]-}2, [HOC]2+{C[C(CN)2]3}2-, [HOC]2+{Ni[S2C2(CF3) 2]22-}2, [HOC]3+{[PF6]-}3, [HOC]3+{[SbF6]-}3, and [HOC]4+{[SbF6]- 4·MeCN have been by studied by single-crystal X-ray diffraction. HOC and [HOC]4+ have essentially equivalent C6-ring C-C bond distances averaging 1.397 and 1.436 Å, respectively. Their average C6-ring C-N distances are 1.416 and 1.318 Å, respectively. The dication, [HOC]2+, has a distorted (Jahn-Teller) structure corresponding to coupled cyanine fragments with distinctly different short (1.395-Å) and long (1.471-Å) C6-ring C-C and C-N (1.337- and 1.405-Å) distances. The 1+ and 3+ radical ions also show distorted structures, although the distortions are smaller than observed for the 2+ structure. The short C6-ring C-C bond distances are 1.382 and 1.417 Å, and the long C6-ring C-C bond distances are 1.444 and 1.439 Å, while the short C6-ring C-N bond distances are 1.371 and 1.326 Å and the long C6-ring C-N bond distances are 1.422 and 1.339 Å, respectively. Solid-state magnetic susceptibility measurements show that the n = 0, 2+, and 4+ compounds are diamagnetic and that the n= 1+ 3+ salts are S = 1/2 paramagnets that obey the Curie-Weiss expression between 2 and 320 K. The effective moments, μeff, and Curie-Weiss constants, are 1.77 and 1.75 μB and θ = -3.3 and -0.9 K for the mono- and trications, respectively. The n = 1+ and 3+ radical cations are fluxional in solution. The EPR spectrum of [HOC]+ in the fast-exchange limit (25°C) shows that all protons N's have the same hyperfine splitting (2.56 G, g = 2.003 15). In the slow-exchange limit (-90°C), arc 2 of 12 equivalent protons (0.974 and 4.222 G) and 6 equivaleat N's (2.595 G). This precludes the observation of a Jahn-Teller distortion in solution. The [HOC]3+ ion is fluxional in solution as it exhibits fast-exchange behavior at -60°C [a(24H) = a(6 N) = 2.81 G; g = 2.0310]. EPR of polycrystalline [HOC]2+ salts show the presence of thermally accessible triplet species whose zero-field splitting parameters are |D| = 0.0550 ±0.0008 cm-1 and |E| = 0.0024 = ±0.0005 cm-1 and are appropriate for triplet states of less than 3-fold symmetry. The temperature of the ΔM = ± 2EPR absorption afforded the seperation between the ground singlet state and the excited triplet state of the dictation for a variety of [HOC]2+ salts. For most counternions, these separations are greater than 3 kcal/mol (1050 cm-1, 0.13 eV), Solid-state magnetic susceptibility measurements for [HOC]2+ with singlet-triplet gaps less 4.0 kcal/mol show in susceptibilities athigher temperatures, consistent with the presence of thermally populated triplet excited states. Magnetic susceptibility amd single-crystal X-ray structures of the dication in the crystalline materials of this study are consistent with a singlet ground state. Molecular orbital (ab initio) calculations are in general agreement with the above results.

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