Aminopolyol-Dependent Assembly of Heterometallic Lanthanide–Iron–Oxo Clusters
journal contribution
posted on 2022-12-07, 21:06 authored by Shan-Shan Chen, Xiu-Ying Zheng, HaiQuan Tian, La-Sheng Long, Lan-Sun Zheng, Xiang-Jian KongLanthanide–iron clusters usually display interesting
structures
and outstanding magnetic properties. However, due to the high reactivity
(acidity) of the Fe<sup>3+</sup>–H<sub>2</sub>O bond and the
inability to form a terminal oxo ligand, the preparation of high-nuclearity
Ln–Fe clusters is a great challenge. Herein, a series of lanthanide–iron–oxo
clusters with the formulas [Y<sub>6</sub>Fe(HL)<sub>10</sub>(NO<sub>3</sub>)<sub>2</sub>(EG)<sub>2</sub>(μ<sub>3</sub>-OH)<sub>8</sub>(H<sub>2</sub>O)<sub>4</sub>]·ClO<sub>4</sub>·N-H<sub>2</sub>BDEA·2H<sub>2</sub>O (<b>Y</b><sub><b>6</b></sub><b>Fe</b>, <b>1</b>, H<sub>2</sub>L = 3-hydroxypivalic
acid, EG = ethylene glycol, N–H<sub>2</sub>BDEA = 2,2′-(butylimino)diethanol),
[Ln<sub>8</sub>Fe<sub>3</sub>(H<sub>2</sub>TEOA)<sub>2</sub>(HTEOA)<sub>2</sub>(HL)<sub>10</sub>(μ<sub>3</sub>-OH)<sub>9</sub>(μ<sub>2</sub>-OH)(μ<sub>4</sub>-O)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]·(NO<sub>3</sub>)<sub>3</sub>·<i>x</i>H<sub>2</sub>O (Ln = Y, <i>x</i> = 13 for <b>2</b>, <b>Y</b><sub><b>8</b></sub><b>Fe</b><sub><b>3</b></sub>; Ln = Dy, <i>x</i> = 10 for <b>3</b>, <b>Dy</b><sub><b>8</b></sub><b>Fe</b><sub><b>3</b></sub>; H<sub>3</sub>TEOA = triethanolamine), and [Ln<sub>12</sub>Fe<sub>14</sub>(HL)<sub>16</sub>(μ<sub>3</sub>-OH)<sub>20</sub>(μ<sub>2</sub>-OH)<sub>12</sub>(μ<sub>4</sub>-O)<sub>12</sub>(H<sub>2</sub>O)<sub>12</sub>]·(NO<sub>3</sub>)<sub>6</sub>·<i>x</i>H<sub>2</sub>O (Ln = Y, <i>x</i> = 40 for <b>4</b>, <b>Y</b><sub><b>12</b></sub><b>Fe</b><sub><b>14</b></sub>; Ln = Dy, <i>x</i> = 30 for <b>5</b>, <b>Dy</b><sub><b>12</b></sub><b>Fe</b><sub><b>14</b></sub>) were obtained by
adjusting the pH with different aminopolyols as organic alkalis. Structural
analysis showed that a cubane-like unit was the main structural unit
in compounds <b>1</b>–<b>5</b>. Compound <b>1</b> was formed by two {Y<sub>3</sub>Fe(μ<sub>3</sub>-OH)<sub>4</sub>} units with the common vertices, and compounds <b>2</b> and <b>3</b> were formed by two {Y<sub>3</sub>Fe(μ<sub>3</sub>-OH)<sub>3</sub>(μ<sub>4</sub>-O)} units with the common
vertices bridging a quadrilateral unit {Ln<sub>2</sub>Fe<sub>2</sub>(μ<sub>3</sub>-OH)<sub>3</sub>(μ<sub>2</sub>-OH)}. The
basic structural units of cubane-like {Ln<sub>2</sub>Fe<sub>2</sub>(μ<sub>3</sub>-OH)(μ<sub>4</sub>-O)<sub>3</sub>}, triangular
{LnFe<sub>2</sub>(μ<sub>3</sub>-OH)<sub>2</sub>(μ<sub>4</sub>-O)}, and neutral iron–hydroxyl {Fe(μ<sub>3</sub>-OH)(μ<sub>2</sub>-OH)<sub>2</sub>} were found in compounds <b>4</b> and <b>5</b>. The universality of building blocks
for the assembly has been demonstrated in high-nuclearity lanthanide–iron–oxo
clusters. Meanwhile, the structural regulation of the lanthanide–iron–oxo
clusters <b>1</b>–<b>5</b> was realized by adjusting
the pH with different organic alkalis, which provided the reference
for the effective synthesis of high-nuclearity lanthanide–iron–oxo
clusters. Magnetic studies showed that <b>3</b> and <b>5</b> displayed a slow magnetic relaxation behavior.
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terminal oxo ligandoutstanding magnetic propertiesmagnetic studies showedstructural analysis showed8 </ sub6 </ sub12 </ sub2 ′-( butylimino5 </ b4 </ b1 </ bhl )< subbasic structural unitsmain structural unit2 </ subn – hcommon vertices bridgingbdea · 2h2 </ b3 </ sub3 </ bdifferent organic alkalisteoa )< sub)< suborganic alkaliscommon verticesx </structural regulation(< bdifferent aminopolyols)} unitsquadrilateral unittriethanolamine ),hydroxypivalic acidgreat challengeethylene glycoleffective synthesisdiethanol ),building blocks
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