Novel Concentration-Driven Structural Interconversion in Shape-Specific Solids Supported by the Octahedral [Re<sub>6</sub>(μ<sub>3</sub>-Se)<sub>8</sub>]<sup>2+</sup> Cluster Core

A complex containing the face-capped octahedral [Re<sub>6</sub>(μ<sub>3</sub>-Se)<sub>8</sub>]<sup>2+</sup> cluster core, <i>cis</i>-[Re<sub>6</sub>(μ<sub>3</sub>-Se)<sub>8</sub>(PPh<sub>3</sub>)<sub>4</sub>(4,4‘-dipyridyl)<sub>2</sub>](SbF<sub>6</sub>)<sub>2</sub> (<b>1</b>), is used as a ditopic ligand with an enforced right angle between the two 4,4‘-dipyridyl moieties for the coordination of Cd<sup>2+</sup> ion. Two coordination polymers, [{Re<sub>6</sub>(μ<sub>3</sub>-Se)<sub>8</sub>(PPh<sub>3</sub>)<sub>4</sub>(4,4‘-dipyridyl)<sub>2</sub>}<sub>2</sub>{Cd(NO<sub>3</sub>)<sub>2</sub>}](SbF<sub>6</sub>)<sub>4</sub>·21C<sub>4</sub>H<sub>1</sub><sub>0</sub>O·21CH<sub>2</sub>Cl<sub>2</sub> (<b>2</b>) and [{Re<sub>6</sub>(μ<sub>3</sub>-Se)<sub>8</sub>(PPh<sub>3</sub>)<sub>4</sub>(4,4‘-dipyridyl)<sub>2</sub>}{Cd(NO<sub>3</sub>)<sub>3</sub>}](NO<sub>3</sub>)·2C<sub>4</sub>H<sub>10</sub>O·CH<sub>2</sub>Cl<sub>2</sub> (<b>3</b>), are obtained. The relative concentration of Cd<sup>2+</sup> determines which species is isolated, and the conversion of the first structure into the second is demonstrated experimentally.