Tetranuclear lanthanide(III) complexes in a seesaw geometry: Synthesis, structure, and magnetism

Joydeb Goura; James P S Walsh; Floriana Tuna; Vadapalli Chandrasekhar

doi:10.1021/ic4027915

Tetranuclear lanthanide(III) complexes in a seesaw geometry: Synthesis, structure, and magnetism

Joydeb Goura, James P S Walsh, Floriana Tuna, Vadapalli Chandrasekhar

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

Abstract

The reaction of 2-methoxy-6-(pyridin-2-ylhydrazonomethyl)phenol (LH) with Ln(III) (Ln = Gd, Tb, Dy, Ho) salts in the presence of an excess of triethylamine afforded [Gd4(L)4(μ4-OH) (μ3-OH)2(NO3)4]·(NO 3)·4CH3CN·CH3OH·2H 2O (1), [Tb4(L)4(μ4-OH) (μ3-OH)2(NO3)4]·(NO 3)·4CH3CN·3H2O (2), [Dy 4(L)4(μ4-OH)(μ3-OH) 2(NO3)4]·(NO3) ·6CH3CN·H2O (3), and [Ho4(L) 4(μ4-OH)(μ-OH)2(NO3) 4]·(NO3)·8CH3CN·3CH 3OH·2H2O (4). All four complexes contain a monocationic tetranuclear core with a unique seesaw topology. The tetranuclear assembly is formed through the coordination of four [L]-, one μ4-OH, two μ3-OH, and four chelating nitrate ligands, with a charge-balancing nitrate counteranion. Magnetic studies reveal a weak antiferromagnetic coupling throughout the series. Compound 1 can be modeled well with an isotropic exchange between all centers parametrized by J = -0.09 cm-1. Compound 3 exhibits slow magnetic relaxation at low temperatures. © 2014 American Chemical Society.

Original language	English
Pages (from-to)	3385-3391
Number of pages	6
Journal	Inorganic Chemistry: including bioinorganic chemistry
Volume	53
Issue number	7
DOIs	https://doi.org/10.1021/ic4027915
Publication status	Published - 7 Apr 2014

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10.1021/ic4027915

CCDC 1004008: Experimental Crystal Structure Determination
Goura, J. (Contributor), Walsh, J. P. S. (Contributor), Tuna, F. (Contributor) & Chandrasekhar, V. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2014
DOI: 10.5517/cc12prcw, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc12prcw&sid=DataCite
Dataset
CCDC 1004005: Experimental Crystal Structure Determination
Goura, J. (Contributor), Walsh, J. P. S. (Contributor), Tuna, F. (Contributor) & Chandrasekhar, V. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2014
DOI: 10.5517/cc12pr8s, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc12pr8s&sid=DataCite
Dataset
CCDC 1004007: Experimental Crystal Structure Determination
Goura, J. (Contributor), Walsh, J. P. S. (Contributor), Tuna, F. (Contributor) & Chandrasekhar, V. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2014
DOI: 10.5517/cc12prbv, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc12prbv&sid=DataCite
Dataset

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@article{9a2d1b4a090b4c9ca567a252ba974341,

title = "Tetranuclear lanthanide(III) complexes in a seesaw geometry: Synthesis, structure, and magnetism",

abstract = "The reaction of 2-methoxy-6-(pyridin-2-ylhydrazonomethyl)phenol (LH) with Ln(III) (Ln = Gd, Tb, Dy, Ho) salts in the presence of an excess of triethylamine afforded [Gd4(L)4(μ4-OH) (μ3-OH)2(NO3)4]·(NO 3)·4CH3CN·CH3OH·2H 2O (1), [Tb4(L)4(μ4-OH) (μ3-OH)2(NO3)4]·(NO 3)·4CH3CN·3H2O (2), [Dy 4(L)4(μ4-OH)(μ3-OH) 2(NO3)4]·(NO3) ·6CH3CN·H2O (3), and [Ho4(L) 4(μ4-OH)(μ-OH)2(NO3) 4]·(NO3)·8CH3CN·3CH 3OH·2H2O (4). All four complexes contain a monocationic tetranuclear core with a unique seesaw topology. The tetranuclear assembly is formed through the coordination of four [L]-, one μ4-OH, two μ3-OH, and four chelating nitrate ligands, with a charge-balancing nitrate counteranion. Magnetic studies reveal a weak antiferromagnetic coupling throughout the series. Compound 1 can be modeled well with an isotropic exchange between all centers parametrized by J = -0.09 cm-1. Compound 3 exhibits slow magnetic relaxation at low temperatures. {\textcopyright} 2014 American Chemical Society.",

author = "Joydeb Goura and Walsh, {James P S} and Floriana Tuna and Vadapalli Chandrasekhar",

year = "2014",

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doi = "10.1021/ic4027915",

language = "English",

volume = "53",

pages = "3385--3391",

journal = "Inorganic Chemistry: including bioinorganic chemistry ",

issn = "0020-1669",

publisher = "American Chemical Society",

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T1 - Tetranuclear lanthanide(III) complexes in a seesaw geometry: Synthesis, structure, and magnetism

AU - Goura, Joydeb

AU - Walsh, James P S

AU - Tuna, Floriana

AU - Chandrasekhar, Vadapalli

PY - 2014/4/7

Y1 - 2014/4/7

N2 - The reaction of 2-methoxy-6-(pyridin-2-ylhydrazonomethyl)phenol (LH) with Ln(III) (Ln = Gd, Tb, Dy, Ho) salts in the presence of an excess of triethylamine afforded [Gd4(L)4(μ4-OH) (μ3-OH)2(NO3)4]·(NO 3)·4CH3CN·CH3OH·2H 2O (1), [Tb4(L)4(μ4-OH) (μ3-OH)2(NO3)4]·(NO 3)·4CH3CN·3H2O (2), [Dy 4(L)4(μ4-OH)(μ3-OH) 2(NO3)4]·(NO3) ·6CH3CN·H2O (3), and [Ho4(L) 4(μ4-OH)(μ-OH)2(NO3) 4]·(NO3)·8CH3CN·3CH 3OH·2H2O (4). All four complexes contain a monocationic tetranuclear core with a unique seesaw topology. The tetranuclear assembly is formed through the coordination of four [L]-, one μ4-OH, two μ3-OH, and four chelating nitrate ligands, with a charge-balancing nitrate counteranion. Magnetic studies reveal a weak antiferromagnetic coupling throughout the series. Compound 1 can be modeled well with an isotropic exchange between all centers parametrized by J = -0.09 cm-1. Compound 3 exhibits slow magnetic relaxation at low temperatures. © 2014 American Chemical Society.

AB - The reaction of 2-methoxy-6-(pyridin-2-ylhydrazonomethyl)phenol (LH) with Ln(III) (Ln = Gd, Tb, Dy, Ho) salts in the presence of an excess of triethylamine afforded [Gd4(L)4(μ4-OH) (μ3-OH)2(NO3)4]·(NO 3)·4CH3CN·CH3OH·2H 2O (1), [Tb4(L)4(μ4-OH) (μ3-OH)2(NO3)4]·(NO 3)·4CH3CN·3H2O (2), [Dy 4(L)4(μ4-OH)(μ3-OH) 2(NO3)4]·(NO3) ·6CH3CN·H2O (3), and [Ho4(L) 4(μ4-OH)(μ-OH)2(NO3) 4]·(NO3)·8CH3CN·3CH 3OH·2H2O (4). All four complexes contain a monocationic tetranuclear core with a unique seesaw topology. The tetranuclear assembly is formed through the coordination of four [L]-, one μ4-OH, two μ3-OH, and four chelating nitrate ligands, with a charge-balancing nitrate counteranion. Magnetic studies reveal a weak antiferromagnetic coupling throughout the series. Compound 1 can be modeled well with an isotropic exchange between all centers parametrized by J = -0.09 cm-1. Compound 3 exhibits slow magnetic relaxation at low temperatures. © 2014 American Chemical Society.

U2 - 10.1021/ic4027915

DO - 10.1021/ic4027915

M3 - Article

SN - 0020-1669

VL - 53

SP - 3385

EP - 3391

JO - Inorganic Chemistry: including bioinorganic chemistry

JF - Inorganic Chemistry: including bioinorganic chemistry

IS - 7

ER -

Tetranuclear lanthanide(III) complexes in a seesaw geometry: Synthesis, structure, and magnetism

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Datasets

CCDC 1004008: Experimental Crystal Structure Determination

CCDC 1004005: Experimental Crystal Structure Determination

CCDC 1004007: Experimental Crystal Structure Determination

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