Surface Modification of High-Nuclearity Lanthanide Clusters:  Two Tetramers Constructed by Cage-Shaped {Dy<sub>26</sub>} Clusters and Isonicotinate Linkers

2007-04-16T00:00:00Z (GMT) by Xiaojun Gu Dongfeng Xue
By incorporation of NO<sub>3</sub><sup>-</sup> ligands with trigonal planar geometry as surface modifiers into the lanthanide cluster core backbone to remarkably improve the dimension of cluster cores, two novel lanthanide cluster compounds, Dy<sub>30</sub>I(μ<sub>3</sub>-OH)<sub>24</sub>(μ<sub>3</sub>-O)<sub>6</sub>(NO<sub>3</sub>)<sub>9</sub>(IN)<sub>41</sub>(OH)<sub>3</sub>(H<sub>2</sub>O)<sub>38</sub> (<b>1</b>) and Dy<sub>104</sub>I<sub>4</sub>(μ<sub>3</sub>-OH)<sub>80</sub>(μ<sub>3</sub>-O)<sub>24</sub>(NO<sub>3</sub>)<sub>36</sub>(IN)<sub>125</sub>(OH)<sub>19</sub>(H<sub>2</sub>O)<sub>1</sub><sub>67</sub> (<b>2</b>) (HIN = isonicotinic acid), have been obtained under hydrothermal conditions. Single-crystal X-ray diffraction shows that in both cluster compounds, the block blocks of [Dy<sub>26</sub>(μ<sub>3</sub>-OH)<sub>20</sub>(μ<sub>3</sub>-O)<sub>6</sub>(NO<sub>3</sub>)<sub>9</sub>I]<sup>36+</sup>, {Dy<sub>26</sub>}, are the largest cage-shaped lanthanide cluster cores known. Compound <b>1</b> is the first tetramer based on the linkage of two different types of high-nuclearity lanthanide clusters and IN ligands, while compound <b>2</b> represents the first tetramer constructed by {Dy<sub>26</sub>} clusters and IN linkers.