Tuning the Condensation Degree of {FeIII n} Oxo Clusters via Ligand Metathesis, Temperature, and Solvents
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BOTEZAT, Olga, VAN LEUSEN, Jan, KOGERLER, Paul, BACA, Svetlana. Tuning the Condensation Degree of {FeIII n} Oxo Clusters via Ligand Metathesis, Temperature, and Solvents. In: Inorganic Chemistry, 2018, vol. 57, pp. 7904-7913. ISSN 0020-1669. DOI: https://doi.org/10.1021/acs.inorgchem.8b00994
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Inorganic Chemistry
Volumul 57 / 2018 / ISSN 0020-1669

Tuning the Condensation Degree of {FeIII n} Oxo Clusters via Ligand Metathesis, Temperature, and Solvents

DOI: https://doi.org/10.1021/acs.inorgchem.8b00994

Pag. 7904-7913

Botezat Olga12, Van Leusen Jan2, Kogerler Paul2, Baca Svetlana1
 
1 Institute of Applied Physics, Academy of Sciences of Moldova,
2 Institutul de Chimie Anorganică
 
Disponibil în IBN: 8 august 2018


Rezumat

Trinuclear μ3-oxo-centered iron(III) isobutyrate clusters readily react with polyalcohol organic ligands under one-pot synthesis conditions. Depending on the ligand, solvent, and temperature, a range of hexa-, dodeca-, and doicosanuclear iron(III) oxo-hydroxo condensation products, isolated as (mdeaH3)2[Fe6O(thme)4Cl6]·0.5(MeCN)·0.5(H2O) (1), [Fe12O4(OH)2(teda)4(N3)4(MeO)4]N3(NO3)0.5(MeO)0.5·2.5(H2O) (2), [Fe12O6(teda)4Cl8]·6(CHCl3) (3), [Fe22O16(OH)2(O2CCHMe2)18(bdea)6(EtO)2(H2O)2]·2(EtOH)·5(MeCN)·6(H2O) (4), and [Fe22O14(OH)4(O2CCHMe2)18(mdea)6(EtO)2(H2O)2](NO3)2·EtOH·H2O (5), where tedaH4 = N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine; thmeH3 = 1,1,1-tris(hydroxymethyl)ethane; mdeaH2 = N-methyldiethanolamine; and bdeaH2 = N-butyldiethanolamine. Complete carboxylate metathesis in the {Fe3} precursor complexes by thme3- or teda4- and the agglomeration of the formed species under solvothermal conditions afforded carboxylate-free {Fe6} product (1) in MeCN/CH2Cl2 or {Fe12} complexes (2 and 3) in MeOH/EtOH and CHCl3/thf, respectively (thf = tetrahydrofuran). Single-crystal X-ray diffraction analyses revealed that 1 contains a [Fe6O(thme)4Cl6]2- cluster anion with a Lindqvist-type {Fe66-O)} core motif, charge-compensated by two protonated mdeaH3 + cations. 2 comprises a [Fe12O4(OH)2(teda)4(N3)4(MeO)4]2+ cation with a {Fe12O4(OH)2}26+ core, whereas 3 contains a charge-neutral [Fe12O6(teda)4(Cl)8] complex with an {Fe12O6}24+ core. Finally, employing flexible bdeaH2 or mdeaH2 ligands under soft reaction conditions afforded giant {Fe22} oxo-hydroxo complexes (4 and 5) with a central {Fe6} layer sandwiched between two outer {Fe8} groups. Magnetic studies of 1-5 revealed strong antiferromagnetic coupling between the FeIII spin centers in all clusters.

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<cfAbstr cfLangCode='EN' cfTrans='o'><p>Trinuclear &mu;<sub>3</sub>-oxo-centered iron(III) isobutyrate clusters readily react with polyalcohol organic ligands under one-pot synthesis conditions. Depending on the ligand, solvent, and temperature, a range of hexa-, dodeca-, and doicosanuclear iron(III) oxo-hydroxo condensation products, isolated as (mdeaH<sub>3</sub>)<sub>2</sub>[Fe<sub>6</sub>O(thme)<sub>4</sub>Cl<sub>6</sub>]&middot;0.5(MeCN)&middot;0.5(H<sub>2</sub>O) (1), [Fe<sub>12</sub>O<sub>4</sub>(OH)<sub>2</sub>(teda)<sub>4</sub>(N<sub>3</sub>)<sub>4</sub>(MeO)<sub>4</sub>]N<sub>3</sub>(NO<sub>3</sub>)<sub>0.5</sub>(MeO)<sub>0.5</sub>&middot;2.5(H<sub>2</sub>O) (2), [Fe<sub>12</sub>O<sub>6</sub>(teda)<sub>4</sub>Cl<sub>8</sub>]&middot;6(CHCl<sub>3</sub>) (3), [Fe<sub>22</sub>O<sub>16</sub>(OH)<sub>2</sub>(O<sub>2</sub>CCHMe<sub>2</sub>)<sub>18</sub>(bdea)<sub>6</sub>(EtO)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]&middot;2(EtOH)&middot;5(MeCN)&middot;6(H<sub>2</sub>O) (4), and [Fe<sub>22</sub>O<sub>14</sub>(OH)<sub>4</sub>(O<sub>2</sub>CCHMe<sub>2</sub>)<sub>18</sub>(mdea)<sub>6</sub>(EtO)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>](NO<sub>3</sub>)<sub>2</sub>&middot;EtOH&middot;H<sub>2</sub>O (5), where tedaH<sub>4</sub> = N,N,N&prime;,N&prime;-tetrakis(2-hydroxyethyl)ethylenediamine; thmeH<sub>3</sub> = 1,1,1-tris(hydroxymethyl)ethane; mdeaH<sub>2</sub> = N-methyldiethanolamine; and bdeaH<sub>2</sub> = N-butyldiethanolamine. Complete carboxylate metathesis in the {Fe<sub>3</sub>} precursor complexes by thme<sup>3-</sup> or teda<sup>4-</sup> and the agglomeration of the formed species under solvothermal conditions afforded carboxylate-free {Fe<sub>6</sub>} product (1) in MeCN/CH<sub>2</sub>Cl<sub>2</sub> or {Fe<sub>12</sub>} complexes (2 and 3) in MeOH/EtOH and CHCl<sub>3</sub>/thf, respectively (thf = tetrahydrofuran). Single-crystal X-ray diffraction analyses revealed that 1 contains a [Fe<sub>6</sub>O(thme)<sub>4</sub>Cl<sub>6</sub>]<sup>2-</sup> cluster anion with a Lindqvist-type {Fe<sub>6</sub>(&mu;<sub>6</sub>-O)} core motif, charge-compensated by two protonated mdeaH<sub>3</sub> <sup>+</sup> cations. 2 comprises a [Fe<sub>12</sub>O<sub>4</sub>(OH)<sub>2</sub>(teda)<sub>4</sub>(N<sub>3</sub>)<sub>4</sub>(MeO)<sub>4</sub>]<sup>2+</sup> cation with a {Fe<sub>12</sub>O<sub>4</sub>(OH)<sub>2</sub>}<sup>26+</sup> core, whereas 3 contains a charge-neutral [Fe<sub>12</sub>O<sub>6</sub>(teda)<sub>4</sub>(Cl)<sub>8</sub>] complex with an {Fe<sub>12</sub>O<sub>6</sub>}<sup>24+</sup> core. Finally, employing flexible bdeaH<sub>2</sub> or mdeaH<sub>2</sub> ligands under soft reaction conditions afforded giant {Fe<sub>22</sub>} oxo-hydroxo complexes (4 and 5) with a central {Fe<sub>6</sub>} layer sandwiched between two outer {Fe<sub>8</sub>} groups. Magnetic studies of 1-5 revealed strong antiferromagnetic coupling between the Fe<sup>III</sup> spin centers in all clusters.</p></cfAbstr>
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