Spin transition in [Fe(DPEA)(NCS)2], a compound with the new tetradentate ligand (2-Aminoethyl)bis(2-pyridylmethyl)amine (DPEA): crystal structure, magnetic properties, and Mössbauer spectroscopy

Galina S. Matouzenko, Azzedine Bousseksou, Sylvain Lecocq, Petra J. van Koningsbruggen, Monique Perrin, Olivier Kahn, André Collet

Research output: Contribution to journalArticle

Abstract

The new spin transition compound [Fe(II)(DPEA)(NCS)(2)], where DPEA [(2-aminoethyl)bis(2-pyridylmethyl)amine] is a new tetradentate ligand, has been synthesized, and its structure, magnetic properties, and Mössbauer spectra have been investigated. The crystal structure has been determined by X-ray diffraction at 298 K. The compound crystallizes in the monoclinic system, space group is P2(1)/c, with Z = 4,a = 9.358(1) Å, b = 11.812(2) Å, c = 17.135(2) Å, and beta = 94.5(4) degrees. The distorted [FeN(6)] octahedron is formed from four nitrogen atoms belonging to DPEA and two provided by the cis thiocyanate groups. The two pyridine rings of DPEA are in mer positions. Each molecule is linked to its neighbors by hydrogen-bonding interactions as well as by numerous van der Waals contacts supposed to be responsible for the cooperativity of the system. Variable-temperature magnetic susceptibility measurements (20-290 K) have evidenced a relatively abrupt S = 2 right harpoon over left harpoon S = 0 transition centered at T(1/2) = 138 K. The thermal variation of the high spin state fraction observed by Mössbauer spectroscopy is in agreement with that obtained from magnetic susceptibility measurements. The fitting of Mössbauer and magnetic data with the Ising-like model allowed us to determine the energy gap between the high-spin and low-spin states (Delta(eff) = 835 K) and to estimate the variation of the thermodynamic parameters upon spin transition. The calculated variations of enthalpy (DeltaH = 6.76 kJ mol(-)(1)) and entropy (DeltaS = 49 J mol(-)(1) K(-)(1)) associated with the spin transition are in agreement with those previously observed for iron(II) spin-crossover compounds. The spin conversion is found to be close to a first-order phenomenon.
Original languageEnglish
Pages (from-to)2975-2981
Number of pages7
JournalInorganic Chemistry
Volume36
Issue number14
DOIs
Publication statusPublished - 2 Jul 1997

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Magnetic susceptibility
Amines
Magnetic properties
amines
Crystal structure
Spectroscopy
magnetic properties
Ligands
ligands
crystal structure
spectroscopy
Enthalpy
Hydrogen bonds
Energy gap
Entropy
Nitrogen
Iron
Thermodynamics
X ray diffraction
Atoms

Cite this

@article{5f3fa49a72f74ebeada4d7976e1a4f7b,
title = "Spin transition in [Fe(DPEA)(NCS)2], a compound with the new tetradentate ligand (2-Aminoethyl)bis(2-pyridylmethyl)amine (DPEA): crystal structure, magnetic properties, and M{\"o}ssbauer spectroscopy",
abstract = "The new spin transition compound [Fe(II)(DPEA)(NCS)(2)], where DPEA [(2-aminoethyl)bis(2-pyridylmethyl)amine] is a new tetradentate ligand, has been synthesized, and its structure, magnetic properties, and M{\"o}ssbauer spectra have been investigated. The crystal structure has been determined by X-ray diffraction at 298 K. The compound crystallizes in the monoclinic system, space group is P2(1)/c, with Z = 4,a = 9.358(1) {\AA}, b = 11.812(2) {\AA}, c = 17.135(2) {\AA}, and beta = 94.5(4) degrees. The distorted [FeN(6)] octahedron is formed from four nitrogen atoms belonging to DPEA and two provided by the cis thiocyanate groups. The two pyridine rings of DPEA are in mer positions. Each molecule is linked to its neighbors by hydrogen-bonding interactions as well as by numerous van der Waals contacts supposed to be responsible for the cooperativity of the system. Variable-temperature magnetic susceptibility measurements (20-290 K) have evidenced a relatively abrupt S = 2 right harpoon over left harpoon S = 0 transition centered at T(1/2) = 138 K. The thermal variation of the high spin state fraction observed by M{\"o}ssbauer spectroscopy is in agreement with that obtained from magnetic susceptibility measurements. The fitting of M{\"o}ssbauer and magnetic data with the Ising-like model allowed us to determine the energy gap between the high-spin and low-spin states (Delta(eff) = 835 K) and to estimate the variation of the thermodynamic parameters upon spin transition. The calculated variations of enthalpy (DeltaH = 6.76 kJ mol(-)(1)) and entropy (DeltaS = 49 J mol(-)(1) K(-)(1)) associated with the spin transition are in agreement with those previously observed for iron(II) spin-crossover compounds. The spin conversion is found to be close to a first-order phenomenon.",
author = "Matouzenko, {Galina S.} and Azzedine Bousseksou and Sylvain Lecocq and {van Koningsbruggen}, {Petra J.} and Monique Perrin and Olivier Kahn and Andr{\'e} Collet",
year = "1997",
month = "7",
day = "2",
doi = "10.1021/ic9615133",
language = "English",
volume = "36",
pages = "2975--2981",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "14",

}

Spin transition in [Fe(DPEA)(NCS)2], a compound with the new tetradentate ligand (2-Aminoethyl)bis(2-pyridylmethyl)amine (DPEA) : crystal structure, magnetic properties, and Mössbauer spectroscopy. / Matouzenko, Galina S.; Bousseksou, Azzedine; Lecocq, Sylvain; van Koningsbruggen, Petra J.; Perrin, Monique; Kahn, Olivier; Collet, André.

In: Inorganic Chemistry, Vol. 36, No. 14, 02.07.1997, p. 2975-2981.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Spin transition in [Fe(DPEA)(NCS)2], a compound with the new tetradentate ligand (2-Aminoethyl)bis(2-pyridylmethyl)amine (DPEA)

T2 - crystal structure, magnetic properties, and Mössbauer spectroscopy

AU - Matouzenko, Galina S.

AU - Bousseksou, Azzedine

AU - Lecocq, Sylvain

AU - van Koningsbruggen, Petra J.

AU - Perrin, Monique

AU - Kahn, Olivier

AU - Collet, André

PY - 1997/7/2

Y1 - 1997/7/2

N2 - The new spin transition compound [Fe(II)(DPEA)(NCS)(2)], where DPEA [(2-aminoethyl)bis(2-pyridylmethyl)amine] is a new tetradentate ligand, has been synthesized, and its structure, magnetic properties, and Mössbauer spectra have been investigated. The crystal structure has been determined by X-ray diffraction at 298 K. The compound crystallizes in the monoclinic system, space group is P2(1)/c, with Z = 4,a = 9.358(1) Å, b = 11.812(2) Å, c = 17.135(2) Å, and beta = 94.5(4) degrees. The distorted [FeN(6)] octahedron is formed from four nitrogen atoms belonging to DPEA and two provided by the cis thiocyanate groups. The two pyridine rings of DPEA are in mer positions. Each molecule is linked to its neighbors by hydrogen-bonding interactions as well as by numerous van der Waals contacts supposed to be responsible for the cooperativity of the system. Variable-temperature magnetic susceptibility measurements (20-290 K) have evidenced a relatively abrupt S = 2 right harpoon over left harpoon S = 0 transition centered at T(1/2) = 138 K. The thermal variation of the high spin state fraction observed by Mössbauer spectroscopy is in agreement with that obtained from magnetic susceptibility measurements. The fitting of Mössbauer and magnetic data with the Ising-like model allowed us to determine the energy gap between the high-spin and low-spin states (Delta(eff) = 835 K) and to estimate the variation of the thermodynamic parameters upon spin transition. The calculated variations of enthalpy (DeltaH = 6.76 kJ mol(-)(1)) and entropy (DeltaS = 49 J mol(-)(1) K(-)(1)) associated with the spin transition are in agreement with those previously observed for iron(II) spin-crossover compounds. The spin conversion is found to be close to a first-order phenomenon.

AB - The new spin transition compound [Fe(II)(DPEA)(NCS)(2)], where DPEA [(2-aminoethyl)bis(2-pyridylmethyl)amine] is a new tetradentate ligand, has been synthesized, and its structure, magnetic properties, and Mössbauer spectra have been investigated. The crystal structure has been determined by X-ray diffraction at 298 K. The compound crystallizes in the monoclinic system, space group is P2(1)/c, with Z = 4,a = 9.358(1) Å, b = 11.812(2) Å, c = 17.135(2) Å, and beta = 94.5(4) degrees. The distorted [FeN(6)] octahedron is formed from four nitrogen atoms belonging to DPEA and two provided by the cis thiocyanate groups. The two pyridine rings of DPEA are in mer positions. Each molecule is linked to its neighbors by hydrogen-bonding interactions as well as by numerous van der Waals contacts supposed to be responsible for the cooperativity of the system. Variable-temperature magnetic susceptibility measurements (20-290 K) have evidenced a relatively abrupt S = 2 right harpoon over left harpoon S = 0 transition centered at T(1/2) = 138 K. The thermal variation of the high spin state fraction observed by Mössbauer spectroscopy is in agreement with that obtained from magnetic susceptibility measurements. The fitting of Mössbauer and magnetic data with the Ising-like model allowed us to determine the energy gap between the high-spin and low-spin states (Delta(eff) = 835 K) and to estimate the variation of the thermodynamic parameters upon spin transition. The calculated variations of enthalpy (DeltaH = 6.76 kJ mol(-)(1)) and entropy (DeltaS = 49 J mol(-)(1) K(-)(1)) associated with the spin transition are in agreement with those previously observed for iron(II) spin-crossover compounds. The spin conversion is found to be close to a first-order phenomenon.

UR - http://pubs.acs.org/doi/full/10.1021/ic9615133

U2 - 10.1021/ic9615133

DO - 10.1021/ic9615133

M3 - Article

C2 - 11669946

VL - 36

SP - 2975

EP - 2981

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 14

ER -