Roland, Bryan K. Flora, Ware H. Selby, Hugh D. Armstrong, Neal R. Zheng, Zhiping Dendritic Arrays of [Re<sub>6</sub>(μ<sub>3</sub>-Se)<sub>8</sub>]<sup>2+</sup> Core-Containing Clusters:  Exploratory Synthesis and Electrochemical Studies The reaction between the previously reported site-differentiated cluster solvate [Re<sub>6</sub>(μ<sub>3</sub>-Se)<sub>8</sub>(PEt<sub>3</sub>)<sub>5</sub>(MeCN)](SbF<sub>6</sub>)<sub>2</sub> (<b>1</b>) with pyridyl-based ditopic ligands 4,4‘-trimethylenedipyridine (<b>2</b>), 1,2-bis(4-pyridyl)ethane (<b>3</b>), and (<i>E</i>)-1,2-bis(4-pyridyl)ethene (<b>4</b>) afforded cluster complexes of the general formula [Re<sub>6</sub>(μ<sub>3</sub>-Se)<sub>8</sub>(PEt<sub>3</sub>)<sub>5</sub>(L)](SbF<sub>6</sub>)<sub>2</sub> (<b>5</b><b>−</b><b>7</b>), where L represents one of the pyridyl-based ligands. Reacting these cluster complex-based ligands with the fully solvated cluster complex [Re<sub>6</sub>(μ<sub>3</sub>-Se)<sub>8</sub>(MeCN)<sub>6</sub>](SbF<sub>6</sub>)<sub>2</sub> (<b>8</b>) produced dendritic arrays of the general formula {Re<sub>6</sub>(μ<sub>3</sub>-Se)<sub>8</sub>[Re<sub>6</sub>(μ<sub>3</sub>-Se)<sub>8</sub>(PEt<sub>3</sub>)<sub>5</sub>(L)]<sub>6</sub>}(SbF<sub>6</sub>)<sub>14</sub> (<b>9</b><b>−</b><b>11</b>), each featuring six circumjacent [Re<sub>6</sub>(μ<sub>3</sub>-Se)<sub>8</sub>(PEt<sub>3</sub>)<sub>5</sub>]<sup>2+</sup> units bridged to a [Re<sub>6</sub>(μ<sub>3</sub>-Se)<sub>8</sub>]<sup>2+</sup> core cluster by the pyridyl-based ligands. Electrochemical studies using a thin-layer electrochemical cell revealed cluster-based redox events in these cluster arrays. For <b>9 </b>(L = <b>2</b>), one reversible oxidation event corresponding to the removal of 7 electrons was observed, indicating noninteraction or extremely weak interactions between the clusters. For <b>10 </b>(L = <b>3</b>), two poorly resolved oxidation waves were found. For <b>11 </b>(L = <b>4</b>), two reversible oxidation events, corresponding respectively to the removal of 1 and 6 electrons, were observed with the 1-electron oxidation event occurring at a potential 150 mV more positive than the 6-electron oxidation. These electrochemical studies suggest intercluster coupling in <b>11</b> via through-bond electronic delocalization, which is consistent with electronic spectroscopic studies of this same molecule. Re;electron;oxidation;ligand;PEt 3;Se;cluster 2006-05-24
    https://acs.figshare.com/articles/journal_contribution/Dendritic_Arrays_of_Re_sub_6_sub_sub_3_sub_Se_sub_8_sub_sup_2_sup_Core_Containing_Clusters_Exploratory_Synthesis_and_Electrochemical_Studies/3221119
10.1021/ja057548w.s002