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 654 2 |
| Ultima descărcare din IBN: 2019-07-27 10:08 |
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| 546 (512) |
| Chimie anorganică (450) |
 SM ISO690:2012DARII, Maxim, KRAVTSOV, Victor, AFFRONTE, M., BACA, Svetlana. Giant {Mn26Tb6} and {Mn26Ho6} heterometallic oxo-hydroxo-carboxylate nanoclusters. In: Materials Science and Condensed Matter Physics, Ed. 9, 25-28 septembrie 2018, Chișinău. Chișinău, Republica Moldova: Institutul de Fizică Aplicată, 2018, Ediția 9, p. 124. |
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| Materials Science and Condensed Matter Physics Ediția 9, 2018 |
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Conferința "International Conference on Materials Science and Condensed Matter Physics" 9, Chișinău, Moldova, 25-28 septembrie 2018 | ||||||
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| CZU: 546 | ||||||
| Pag. 124-124 | ||||||
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The development of new synthetic pathways to assemble novel 3d-4f heterometallic nanoclusters is a considerable challenge. Incorporating lanthanide ions that play a special role in the field of single-molecule magnetism in such molecular clusters provides good starting ingredients for the syntheses of 3d/4f single-molecule magnets. In continuation of our research on the construction of heterometallic 3d-4f clusters [1] we present herein an appealing route for the synthesis of Mn-Tb/Ho nanoclusters with the highest-nuclearity known by today from a smaller hexanuclear {Mn6} isobutyrate precursor. Two new mixed-valent heterometallic dotriacontanuclear MnII,III-LnIII coordination nanoclusters [Mn26Ln6O16(OH)12(O2CCH(CH3)2)42] (LnIII = Tb (1), Ho (2)) with ca. 3.4 x 1.8 nm size have been synthesized and characterized by IR spectroscopy and X-ray diffraction analysis. The compounds are isostructural and crystallize in the orthorhombic space group Pnna with a = 28.177(1), b = 58.315(1), c = 16.089(1) Å, Z = 4, V = 26437(1) Å3 (1) and a = 28.297(1), b = 58.583(1), c = 15.948(1) Å, Z = 4, V = 26437(1) Å3 (2). The clusters reside on two-fold rotation axes and possess C2 molecular symmetry. They comprise a [MnII10MnIII16LnIII6]86+ core, bridged by fourteen μ4-O, two μ3-O, twelve OH groups, and encapsulated by forty-two bridging isobutyrate moieties (Figures 1). Charge consideration of clusters 1 and 2 and BVS calculations indicate that 16 Mn centers are in the +3 oxidation state (Mn1, Mn2, Mn4, Mn5, Mn7, Mn8, Mn10 and Mn12), whereas the remaining 10 Mn centres are in the +2 oxidation state (Mn3, Mn6, Mn9, Mn11 and Mn13). Interestingly, Mn atoms are six-coordinated while Dy atoms are either eight- or nine-coordinated in 1 and 2. Magnetic studies reveal that 1 exhibits single-molecule characteristics up to 12 K. Figure 1. Structure of [Mn26Tb6O16(OH)12(O2CCH(CH3)2)42] cluster. Methyl groups and H atoms are omitted for clarity. |
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Dublin Core Export
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<dc:creator>Darii, M.V.</dc:creator>
<dc:creator>Kravţov, V.H.</dc:creator>
<dc:creator>Affronte, M.</dc:creator>
<dc:creator>Baca, S.G.</dc:creator>
<dc:date>2018</dc:date>
<dc:description xml:lang='en'><p>The development of new synthetic pathways to assemble novel 3d-4f heterometallic nanoclusters is a considerable challenge. Incorporating lanthanide ions that play a special role in the field of single-molecule magnetism in such molecular clusters provides good starting ingredients for the syntheses of 3d/4f single-molecule magnets. In continuation of our research on the construction of heterometallic 3d-4f clusters [1] we present herein an appealing route for the synthesis of Mn-Tb/Ho nanoclusters with the highest-nuclearity known by today from a smaller hexanuclear {Mn6} isobutyrate precursor. Two new mixed-valent heterometallic dotriacontanuclear MnII,III-LnIII coordination nanoclusters [Mn26Ln6O16(OH)12(O2CCH(CH3)2)42] (LnIII = Tb (<strong>1</strong>), Ho (<strong>2</strong>)) with <em>ca. </em>3.4 x 1.8 nm size have been synthesized and characterized by IR spectroscopy and X-ray diffraction analysis. The compounds are isostructural and crystallize in the orthorhombic space group <em>Pnna </em>with <em>a </em>= 28.177(1), <em>b </em>= 58.315(1), <em>c </em>= 16.089(1) Å, <em>Z </em>= 4, <em>V </em>= 26437(1) Å3 (<strong>1</strong>) and <em>a </em>= 28.297(1), <em>b </em>= 58.583(1), <em>c </em>= 15.948(1) Å, <em>Z </em>= 4, <em>V </em>= 26437(1) Å3 (<strong>2</strong>). The clusters reside on two-fold rotation axes and possess <em>C</em>2 molecular symmetry. They comprise a [MnII10MnIII16LnIII6]86+ core, bridged by fourteen <em>μ</em>4-O, two <em>μ</em>3-O, twelve OH groups, and encapsulated by forty-two bridging isobutyrate moieties (Figures 1). Charge consideration of clusters <strong>1 </strong>and <strong>2 </strong>and BVS calculations indicate that 16 Mn centers are in the +3 oxidation state (Mn1, Mn2, Mn4, Mn5, Mn7, Mn8, Mn10 and Mn12), whereas the remaining 10 Mn centres are in the +2 oxidation state (Mn3, Mn6, Mn9, Mn11 and Mn13). Interestingly, Mn atoms are six-coordinated while Dy atoms are either eight- or nine-coordinated in <strong>1 </strong>and <strong>2. </strong>Magnetic studies reveal that <strong>1 </strong>exhibits single-molecule characteristics up to 12 K. Figure 1. Structure of [Mn26Tb6O16(OH)12(O2CCH(CH3)2)42] cluster. Methyl groups and H atoms are omitted for clarity.</p></dc:description>
<dc:source>Materials Science and Condensed Matter Physics (Ediția 9) 124-124</dc:source>
<dc:title>Giant {Mn26Tb6} and {Mn26Ho6} heterometallic oxo-hydroxo-carboxylate nanoclusters</dc:title>
<dc:type>info:eu-repo/semantics/article</dc:type>
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