Pentameric circular iron(II) double helicates and a molecular pentafoil knot

Jean François Ayme; Jonathon E. Beves; David A. Leigh; Roy T. McBurney; Kari Rissanen; David Schultz

doi:10.1021/ja303355v

Pentameric circular iron(II) double helicates and a molecular pentafoil knot

Jean François Ayme, Jonathon E. Beves, David A. Leigh, Roy T. McBurney, Kari Rissanen, David Schultz

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Abstract

We report on the synthesis of 11 pentameric cyclic helicates formed by imine condensation of alkyl monoamines with a common bis(formylpyridine) bipyridyl-derived building block and iron(II) and chloride ions. The cyclic double-stranded helicates were characterized by NMR spectroscopy, mass spectrometry, and in the case of a 2,4-dimethoxybenzylamine-derived pentameric cyclic helicate, X-ray crystallography. The factors influencing the assembly process (reactant stoichiometry, concentration, solvent, nature and amount of anion) were studied in detail: the role of chloride in the assembly process appears not to be limited to that of a simple template, and larger circular helicates observed with related tris(bipyridine) ligands with different iron salts are not produced with the imine ligands. Using certain chiral amines, pentameric cyclic helices of single handedness could be isolated and the stereochemistry of the helix determined by circular dichroism. By employing a particular diamine, a closed-loop molecular pentafoil knot was prepared. The pentafoil knot was characterized by NMR spectroscopy, mass spectrometry, and X-ray crystallography, confirming the topology and providing insights into the reasons for its formation. © 2012 American Chemical Society.

Original language	English
Pages (from-to)	9488-9497
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	134
Issue number	22
DOIs	https://doi.org/10.1021/ja303355v
Publication status	Published - 6 Jun 2012

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CCDC 845599: Experimental Crystal Structure Determination
Ayme, J. F. (Contributor), Beves, J. E. (Contributor), Leigh, D. (Contributor), McBurney, R. T. (Contributor), Rissanen, K. (Contributor) & Schultz, D. (Contributor), Cambridge Crystallographic Data Centre, 21 Sept 2011
DOI: 10.5517/ccxcxdk, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccxcxdk&sid=DataCite
Dataset
CCDC 875091: Experimental Crystal Structure Determination
Ayme, J. F. (Contributor), Beves, J. E. (Contributor), Leigh, D. (Contributor), McBurney, R. T. (Contributor), Rissanen, K. (Contributor) & Schultz, D. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2012
DOI: 10.5517/ccyclrm, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccyclrm&sid=DataCite
Dataset

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title = "Pentameric circular iron(II) double helicates and a molecular pentafoil knot",

abstract = "We report on the synthesis of 11 pentameric cyclic helicates formed by imine condensation of alkyl monoamines with a common bis(formylpyridine) bipyridyl-derived building block and iron(II) and chloride ions. The cyclic double-stranded helicates were characterized by NMR spectroscopy, mass spectrometry, and in the case of a 2,4-dimethoxybenzylamine-derived pentameric cyclic helicate, X-ray crystallography. The factors influencing the assembly process (reactant stoichiometry, concentration, solvent, nature and amount of anion) were studied in detail: the role of chloride in the assembly process appears not to be limited to that of a simple template, and larger circular helicates observed with related tris(bipyridine) ligands with different iron salts are not produced with the imine ligands. Using certain chiral amines, pentameric cyclic helices of single handedness could be isolated and the stereochemistry of the helix determined by circular dichroism. By employing a particular diamine, a closed-loop molecular pentafoil knot was prepared. The pentafoil knot was characterized by NMR spectroscopy, mass spectrometry, and X-ray crystallography, confirming the topology and providing insights into the reasons for its formation. {\textcopyright} 2012 American Chemical Society.",

author = "Ayme, {Jean Fran{\c c}ois} and Beves, {Jonathon E.} and Leigh, {David A.} and McBurney, {Roy T.} and Kari Rissanen and David Schultz",

note = "ACKNOWLEDGMENTS This research was funded by the EPSRC and the Academy of Finland (K.R., Projects 212588 and 218325).Experimental procedures and spectral data for all compounds and the details of the X-ray analyses of [3bCl](PF6)9·xsolvent and [7Cl](PF6)9·xsolvent including CIF ﬁles. This material is available free of charge via the Internet at http://pubs.acs.org.",

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doi = "10.1021/ja303355v",

language = "English",

volume = "134",

pages = "9488--9497",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

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T1 - Pentameric circular iron(II) double helicates and a molecular pentafoil knot

AU - Ayme, Jean François

AU - Beves, Jonathon E.

AU - Leigh, David A.

AU - McBurney, Roy T.

AU - Rissanen, Kari

AU - Schultz, David

N1 - ACKNOWLEDGMENTS This research was funded by the EPSRC and the Academy of Finland (K.R., Projects 212588 and 218325).Experimental procedures and spectral data for all compounds and the details of the X-ray analyses of [3bCl](PF6)9·xsolvent and [7Cl](PF6)9·xsolvent including CIF ﬁles. This material is available free of charge via the Internet at http://pubs.acs.org.

PY - 2012/6/6

Y1 - 2012/6/6

N2 - We report on the synthesis of 11 pentameric cyclic helicates formed by imine condensation of alkyl monoamines with a common bis(formylpyridine) bipyridyl-derived building block and iron(II) and chloride ions. The cyclic double-stranded helicates were characterized by NMR spectroscopy, mass spectrometry, and in the case of a 2,4-dimethoxybenzylamine-derived pentameric cyclic helicate, X-ray crystallography. The factors influencing the assembly process (reactant stoichiometry, concentration, solvent, nature and amount of anion) were studied in detail: the role of chloride in the assembly process appears not to be limited to that of a simple template, and larger circular helicates observed with related tris(bipyridine) ligands with different iron salts are not produced with the imine ligands. Using certain chiral amines, pentameric cyclic helices of single handedness could be isolated and the stereochemistry of the helix determined by circular dichroism. By employing a particular diamine, a closed-loop molecular pentafoil knot was prepared. The pentafoil knot was characterized by NMR spectroscopy, mass spectrometry, and X-ray crystallography, confirming the topology and providing insights into the reasons for its formation. © 2012 American Chemical Society.

AB - We report on the synthesis of 11 pentameric cyclic helicates formed by imine condensation of alkyl monoamines with a common bis(formylpyridine) bipyridyl-derived building block and iron(II) and chloride ions. The cyclic double-stranded helicates were characterized by NMR spectroscopy, mass spectrometry, and in the case of a 2,4-dimethoxybenzylamine-derived pentameric cyclic helicate, X-ray crystallography. The factors influencing the assembly process (reactant stoichiometry, concentration, solvent, nature and amount of anion) were studied in detail: the role of chloride in the assembly process appears not to be limited to that of a simple template, and larger circular helicates observed with related tris(bipyridine) ligands with different iron salts are not produced with the imine ligands. Using certain chiral amines, pentameric cyclic helices of single handedness could be isolated and the stereochemistry of the helix determined by circular dichroism. By employing a particular diamine, a closed-loop molecular pentafoil knot was prepared. The pentafoil knot was characterized by NMR spectroscopy, mass spectrometry, and X-ray crystallography, confirming the topology and providing insights into the reasons for its formation. © 2012 American Chemical Society.

U2 - 10.1021/ja303355v

DO - 10.1021/ja303355v

M3 - Article

SN - 0002-7863

VL - 134

SP - 9488

EP - 9497

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 22

ER -

Pentameric circular iron(II) double helicates and a molecular pentafoil knot

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CCDC 845599: Experimental Crystal Structure Determination

CCDC 875091: Experimental Crystal Structure Determination

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