A New Tetranuclear Oxohydroxoiron(III) Cluster: Crystal Structure, Magnetic Properties, and Exafs Investigation of [L4Fe4(μ-O)2(μ-OH)4]I4.3H2O (L = 1,4,7-Triazacyclononane)

Stefan Drüeke; Karl Wieghardt; Bernhard Nuber; Johannes Weiss; Emile L. Bominaar; A. Sawaryn; H. Winkler; A. X. Trautwein

doi:10.1021/ic00324a011

A New Tetranuclear Oxohydroxoiron(III) Cluster: Crystal Structure, Magnetic Properties, and Exafs Investigation of [L4Fe4(μ-O)2(μ-OH)4]I4.3H2O (L = 1,4,7-Triazacyclononane)

Stefan Drüeke, Karl Wieghardt^*, Bernhard Nuber, Johannes Weiss, Emile L. Bominaar, A. Sawaryn, H. Winkler, A. X. Trautwein

^*Corresponding author for this work

Institute of Physics

35 Citations (Scopus)

Abstract

Hydrolysis of the cation [L₂Fe₂(acac)₂(μ-O)]²⁺in aqueous solution yields the new tetranuclear species [L₄Fe₄(μ-O)₂μ-OH)₄]⁴⁺, where L represents the cyclic amine 1,4,7-triazacyclononane (L; C₆H_l5N₃) and acac is acetylacetonate(l-). The green tetraiodide trihydrate and the tetraperchlorate trihydrate have been isolated as solid materials. The crystal structure of [L₄Fe₄(μ-O)₂(μ-OH)₄]I₄.3H₂O has been determined by X-ray crystallography. Crystal data: monoclinic; P2₁/a (C2h); a = 14.653 (6) Å; b = 19.092 (7) Å; c = 17.309 (8) Å; = 91.80 (3)°; V = 4839.9 A³; Z = 4. Four ferric ions are connected by two μ₂-oxo and four μ2-hydroxo bridges, forming the distorted adamantane-like core [Fe₄(μ-O)₂(μ-OH)₄]⁴⁺; each Fe^IIIcenter is capped by the tridentate amine L (fac-FeN₃O₃donor set at each Fe^III), The complex may be envisaged as a dimer of the dimer containing a [Fe-0-Fe]⁴⁺core. From temperature-dependent susceptibility measurements strong intramolecular antiferromagnetic coupling between all four high-spin ferric ions is established (S = 0 ground state; J = -106.3 (2) cm^-1and J’= -15.1 (2) cm^-1). EXAFS spectra of the tetraiodide and of the tetraperchlorate are in excellent agreement with the results obtained by crystallography: in particular, the two different intramolecular Fe.Fe distances at 3.33 and 3.53 Å and the differing Fe-O_oxo and Fe-O_hydroxo distances at 1,82 and 2.00 A, respectively, are clearly detected in both salts. In alkaline solution the tetranuclear complex is shown to dissociate, generating most probably two of the binuclear species [LFe(OH)₂(μ-O)Fe(OH)₂L]. The process is reversible; reacidification regenerates the tetranuclear complex.

Original language	English
Journal	Inorganic Chemistry
Volume	28
Issue number	25
Pages (from-to)	4477-4483
Number of pages	7
ISSN	0020-1669
DOIs	https://doi.org/10.1021/ic00324a011
Publication status	Published - 01.12.1989

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Drüeke, S., Wieghardt, K., Nuber, B., Weiss, J., Bominaar, E. L., Sawaryn, A., Winkler, H., & Trautwein, A. X. (1989). A New Tetranuclear Oxohydroxoiron(III) Cluster: Crystal Structure, Magnetic Properties, and Exafs Investigation of [L4Fe4(μ-O)2(μ-OH)4]I4.3H2O (L = 1,4,7-Triazacyclononane). Inorganic Chemistry, 28(25), 4477-4483. https://doi.org/10.1021/ic00324a011

@article{19076dfd524946078da00e7d744cc8c8,

title = "A New Tetranuclear Oxohydroxoiron(III) Cluster: Crystal Structure, Magnetic Properties, and Exafs Investigation of [L4Fe4(μ-O)2(μ-OH)4]I4.3H2O (L = 1,4,7-Triazacyclononane)",

abstract = "Hydrolysis of the cation [L2Fe2(acac)2(μ-O)]2+in aqueous solution yields the new tetranuclear species [L4Fe4(μ-O)2μ-OH)4]4+, where L represents the cyclic amine 1,4,7-triazacyclononane (L; C6Hl5N3) and acac is acetylacetonate(l-). The green tetraiodide trihydrate and the tetraperchlorate trihydrate have been isolated as solid materials. The crystal structure of [L4Fe4(μ-O)2(μ-OH)4]I4.3H2O has been determined by X-ray crystallography. Crystal data: monoclinic; P21/a (C2h); a = 14.653 (6) {\AA}; b = 19.092 (7) {\AA}; c = 17.309 (8) {\AA}; = 91.80 (3)°; V = 4839.9 A3; Z = 4. Four ferric ions are connected by two μ2-oxo and four μ2-hydroxo bridges, forming the distorted adamantane-like core [Fe4(μ-O)2(μ-OH)4]4+; each FeIIIcenter is capped by the tridentate amine L (fac-FeN3O3donor set at each FeIII), The complex may be envisaged as a dimer of the dimer containing a [Fe-0-Fe]4+core. From temperature-dependent susceptibility measurements strong intramolecular antiferromagnetic coupling between all four high-spin ferric ions is established (S = 0 ground state; J = -106.3 (2) cm-1and J{\textquoteright}= -15.1 (2) cm-1). EXAFS spectra of the tetraiodide and of the tetraperchlorate are in excellent agreement with the results obtained by crystallography: in particular, the two different intramolecular Fe.Fe distances at 3.33 and 3.53 {\AA} and the differing Fe-Ooxo and Fe-Ohydroxo distances at 1,82 and 2.00 A, respectively, are clearly detected in both salts. In alkaline solution the tetranuclear complex is shown to dissociate, generating most probably two of the binuclear species [LFe(OH)2(μ-O)Fe(OH)2L]. The process is reversible; reacidification regenerates the tetranuclear complex.",

author = "Stefan Dr{\"u}eke and Karl Wieghardt and Bernhard Nuber and Johannes Weiss and Bominaar, {Emile L.} and A. Sawaryn and H. Winkler and Trautwein, {A. X.}",

year = "1989",

month = dec,

day = "1",

doi = "10.1021/ic00324a011",

language = "English",

volume = "28",

pages = "4477--4483",

journal = "Inorganic Chemistry",

issn = "0020-1669",

number = "25",

}

Drüeke, S, Wieghardt, K, Nuber, B, Weiss, J, Bominaar, EL, Sawaryn, A, Winkler, H & Trautwein, AX 1989, 'A New Tetranuclear Oxohydroxoiron(III) Cluster: Crystal Structure, Magnetic Properties, and Exafs Investigation of [L4Fe4(μ-O)2(μ-OH)4]I4.3H2O (L = 1,4,7-Triazacyclononane)', Inorganic Chemistry, vol. 28, no. 25, pp. 4477-4483. https://doi.org/10.1021/ic00324a011

A New Tetranuclear Oxohydroxoiron(III) Cluster: Crystal Structure, Magnetic Properties, and Exafs Investigation of [L4Fe4(μ-O)2(μ-OH)4]I4.3H2O (L = 1,4,7-Triazacyclononane). / Drüeke, Stefan; Wieghardt, Karl; Nuber, Bernhard et al.
In: Inorganic Chemistry, Vol. 28, No. 25, 01.12.1989, p. 4477-4483.

Research output: Journal Articles › Journal articles › Research › peer-review

TY - JOUR

T1 - A New Tetranuclear Oxohydroxoiron(III) Cluster: Crystal Structure, Magnetic Properties, and Exafs Investigation of [L4Fe4(μ-O)2(μ-OH)4]I4.3H2O (L = 1,4,7-Triazacyclononane)

AU - Drüeke, Stefan

AU - Wieghardt, Karl

AU - Nuber, Bernhard

AU - Weiss, Johannes

AU - Bominaar, Emile L.

AU - Sawaryn, A.

AU - Winkler, H.

AU - Trautwein, A. X.

PY - 1989/12/1

Y1 - 1989/12/1

N2 - Hydrolysis of the cation [L2Fe2(acac)2(μ-O)]2+in aqueous solution yields the new tetranuclear species [L4Fe4(μ-O)2μ-OH)4]4+, where L represents the cyclic amine 1,4,7-triazacyclononane (L; C6Hl5N3) and acac is acetylacetonate(l-). The green tetraiodide trihydrate and the tetraperchlorate trihydrate have been isolated as solid materials. The crystal structure of [L4Fe4(μ-O)2(μ-OH)4]I4.3H2O has been determined by X-ray crystallography. Crystal data: monoclinic; P21/a (C2h); a = 14.653 (6) Å; b = 19.092 (7) Å; c = 17.309 (8) Å; = 91.80 (3)°; V = 4839.9 A3; Z = 4. Four ferric ions are connected by two μ2-oxo and four μ2-hydroxo bridges, forming the distorted adamantane-like core [Fe4(μ-O)2(μ-OH)4]4+; each FeIIIcenter is capped by the tridentate amine L (fac-FeN3O3donor set at each FeIII), The complex may be envisaged as a dimer of the dimer containing a [Fe-0-Fe]4+core. From temperature-dependent susceptibility measurements strong intramolecular antiferromagnetic coupling between all four high-spin ferric ions is established (S = 0 ground state; J = -106.3 (2) cm-1and J’= -15.1 (2) cm-1). EXAFS spectra of the tetraiodide and of the tetraperchlorate are in excellent agreement with the results obtained by crystallography: in particular, the two different intramolecular Fe.Fe distances at 3.33 and 3.53 Å and the differing Fe-Ooxo and Fe-Ohydroxo distances at 1,82 and 2.00 A, respectively, are clearly detected in both salts. In alkaline solution the tetranuclear complex is shown to dissociate, generating most probably two of the binuclear species [LFe(OH)2(μ-O)Fe(OH)2L]. The process is reversible; reacidification regenerates the tetranuclear complex.

AB - Hydrolysis of the cation [L2Fe2(acac)2(μ-O)]2+in aqueous solution yields the new tetranuclear species [L4Fe4(μ-O)2μ-OH)4]4+, where L represents the cyclic amine 1,4,7-triazacyclononane (L; C6Hl5N3) and acac is acetylacetonate(l-). The green tetraiodide trihydrate and the tetraperchlorate trihydrate have been isolated as solid materials. The crystal structure of [L4Fe4(μ-O)2(μ-OH)4]I4.3H2O has been determined by X-ray crystallography. Crystal data: monoclinic; P21/a (C2h); a = 14.653 (6) Å; b = 19.092 (7) Å; c = 17.309 (8) Å; = 91.80 (3)°; V = 4839.9 A3; Z = 4. Four ferric ions are connected by two μ2-oxo and four μ2-hydroxo bridges, forming the distorted adamantane-like core [Fe4(μ-O)2(μ-OH)4]4+; each FeIIIcenter is capped by the tridentate amine L (fac-FeN3O3donor set at each FeIII), The complex may be envisaged as a dimer of the dimer containing a [Fe-0-Fe]4+core. From temperature-dependent susceptibility measurements strong intramolecular antiferromagnetic coupling between all four high-spin ferric ions is established (S = 0 ground state; J = -106.3 (2) cm-1and J’= -15.1 (2) cm-1). EXAFS spectra of the tetraiodide and of the tetraperchlorate are in excellent agreement with the results obtained by crystallography: in particular, the two different intramolecular Fe.Fe distances at 3.33 and 3.53 Å and the differing Fe-Ooxo and Fe-Ohydroxo distances at 1,82 and 2.00 A, respectively, are clearly detected in both salts. In alkaline solution the tetranuclear complex is shown to dissociate, generating most probably two of the binuclear species [LFe(OH)2(μ-O)Fe(OH)2L]. The process is reversible; reacidification regenerates the tetranuclear complex.

UR - http://www.scopus.com/inward/record.url?scp=0001546625&partnerID=8YFLogxK

U2 - 10.1021/ic00324a011

DO - 10.1021/ic00324a011

M3 - Journal articles

AN - SCOPUS:0001546625

SN - 0020-1669

VL - 28

SP - 4477

EP - 4483

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 25

ER -

A New Tetranuclear Oxohydroxoiron(III) Cluster: Crystal Structure, Magnetic Properties, and Exafs Investigation of [L4Fe4(μ-O)2(μ-OH)4]I4.3H2O (L = 1,4,7-Triazacyclononane)

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