Di- and trivalent iron complexes with redox-active 1-(2-pyridylazo)-2-phenanthrol (papl)

Robin A. Taylor; Alan J. Lough; Takele Seda; Prashanth K. Poddutoori; Martin T. Lemaire

doi:10.1016/j.poly.2016.11.044

Di- and trivalent iron complexes with redox-active 1-(2-pyridylazo)-2-phenanthrol (papl)

Robin A. Taylor, Alan J. Lough, Takele Seda, Prashanth K. Poddutoori, Martin T. Lemaire

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

6 Scopus citations

Abstract

The synthesis and study of redox-active ligand complexes has received much recent attention. We have recently explored the coordination chemistry of arylazo redox-active ligand 1-(2-pyridylazo)-2-phenanthrol (papl) and herein expand the series of complexes to the Group 8 transition metal ion, iron. We report the preparation and structure of a divalent iron complex with the papl anion, Fe(papl)₂, which is diamagnetic and features ligand centered redox activity and intense visible electronic transitions. Three polymorphs of the Fe(papl)₂complex are reported, including one that exhibits a structural phase transition at low temperature. Oxidation of Fe(papl)₂with molecular iodine has produced the low-spin trivalent complex [Fe³⁺(papl)₂]⁺as an ionic complex with the I₃anion. Density functional theory (dft) calculations and data from variable temperature Mössbauer spectroscopy experiments are provided to shed light on the electronic structures of these iron complexes.

Original language	English (US)
Pages (from-to)	462-469
Number of pages	8
Journal	Polyhedron
Volume	123
DOIs	https://doi.org/10.1016/j.poly.2016.11.044
State	Published - 2017
Externally published	Yes

Bibliographical note

Funding Information:
MTL acknowledges funding from NSERC, Cummings Foundation (CFI), Canada Research Chairs Program, Brandon and Brock University and the University of Manitoba for providing an adjunct position. MTL thanks Prof. Art van der Est (Brock University) for the use of the EPR facility. TS thanks the Department of Physics & Astronomy at Western Washington University for support of this work.

Publisher Copyright:
© 2016 Elsevier Ltd

Keywords

Density functional theory
Iron complexes
Mössbauer spectroscopy
Redox active ligands
X-ray crystallography

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10.1016/j.poly.2016.11.044

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title = "Di- and trivalent iron complexes with redox-active 1-(2-pyridylazo)-2-phenanthrol (papl)",

abstract = "The synthesis and study of redox-active ligand complexes has received much recent attention. We have recently explored the coordination chemistry of arylazo redox-active ligand 1-(2-pyridylazo)-2-phenanthrol (papl) and herein expand the series of complexes to the Group 8 transition metal ion, iron. We report the preparation and structure of a divalent iron complex with the papl anion, Fe(papl)2, which is diamagnetic and features ligand centered redox activity and intense visible electronic transitions. Three polymorphs of the Fe(papl)2complex are reported, including one that exhibits a structural phase transition at low temperature. Oxidation of Fe(papl)2with molecular iodine has produced the low-spin trivalent complex [Fe3+(papl)2]+as an ionic complex with the I3anion. Density functional theory (dft) calculations and data from variable temperature M{\"o}ssbauer spectroscopy experiments are provided to shed light on the electronic structures of these iron complexes.",

keywords = "Density functional theory, Iron complexes, M{\"o}ssbauer spectroscopy, Redox active ligands, X-ray crystallography",

author = "Taylor, {Robin A.} and Lough, {Alan J.} and Takele Seda and Poddutoori, {Prashanth K.} and Lemaire, {Martin T.}",

note = "Funding Information: MTL acknowledges funding from NSERC, Cummings Foundation (CFI), Canada Research Chairs Program, Brandon and Brock University and the University of Manitoba for providing an adjunct position. MTL thanks Prof. Art van der Est (Brock University) for the use of the EPR facility. TS thanks the Department of Physics & Astronomy at Western Washington University for support of this work. Publisher Copyright: {\textcopyright} 2016 Elsevier Ltd",

year = "2017",

doi = "10.1016/j.poly.2016.11.044",

language = "English (US)",

volume = "123",

pages = "462--469",

journal = "Polyhedron",

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T1 - Di- and trivalent iron complexes with redox-active 1-(2-pyridylazo)-2-phenanthrol (papl)

AU - Taylor, Robin A.

AU - Lough, Alan J.

AU - Seda, Takele

AU - Poddutoori, Prashanth K.

AU - Lemaire, Martin T.

N1 - Funding Information: MTL acknowledges funding from NSERC, Cummings Foundation (CFI), Canada Research Chairs Program, Brandon and Brock University and the University of Manitoba for providing an adjunct position. MTL thanks Prof. Art van der Est (Brock University) for the use of the EPR facility. TS thanks the Department of Physics & Astronomy at Western Washington University for support of this work. Publisher Copyright: © 2016 Elsevier Ltd

PY - 2017

Y1 - 2017

N2 - The synthesis and study of redox-active ligand complexes has received much recent attention. We have recently explored the coordination chemistry of arylazo redox-active ligand 1-(2-pyridylazo)-2-phenanthrol (papl) and herein expand the series of complexes to the Group 8 transition metal ion, iron. We report the preparation and structure of a divalent iron complex with the papl anion, Fe(papl)2, which is diamagnetic and features ligand centered redox activity and intense visible electronic transitions. Three polymorphs of the Fe(papl)2complex are reported, including one that exhibits a structural phase transition at low temperature. Oxidation of Fe(papl)2with molecular iodine has produced the low-spin trivalent complex [Fe3+(papl)2]+as an ionic complex with the I3anion. Density functional theory (dft) calculations and data from variable temperature Mössbauer spectroscopy experiments are provided to shed light on the electronic structures of these iron complexes.

AB - The synthesis and study of redox-active ligand complexes has received much recent attention. We have recently explored the coordination chemistry of arylazo redox-active ligand 1-(2-pyridylazo)-2-phenanthrol (papl) and herein expand the series of complexes to the Group 8 transition metal ion, iron. We report the preparation and structure of a divalent iron complex with the papl anion, Fe(papl)2, which is diamagnetic and features ligand centered redox activity and intense visible electronic transitions. Three polymorphs of the Fe(papl)2complex are reported, including one that exhibits a structural phase transition at low temperature. Oxidation of Fe(papl)2with molecular iodine has produced the low-spin trivalent complex [Fe3+(papl)2]+as an ionic complex with the I3anion. Density functional theory (dft) calculations and data from variable temperature Mössbauer spectroscopy experiments are provided to shed light on the electronic structures of these iron complexes.

KW - Density functional theory

KW - Iron complexes

KW - Mössbauer spectroscopy

KW - Redox active ligands

KW - X-ray crystallography

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JO - Polyhedron

JF - Polyhedron

ER -

Di- and trivalent iron complexes with redox-active 1-(2-pyridylazo)-2-phenanthrol (papl)

Abstract

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