Postsynthetic
Exchanges of the Pillaring Ligand in
Three-Dimensional Metal–Organic Frameworks
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Abstract
Metal–organic frameworks,
[Ni(HBTC)(dabco)] (<b>2</b>) and [Ni<sub>2</sub>(HBTC)<sub>2</sub>(bipy)<sub>0.6</sub>(dabco)<sub>1.4</sub>] (<b>3</b>) (where
H<sub>3</sub>BTC is 1,3,5-benzenetricarboxylic
acid, dabco is 1,4-diazabicyclo[2.2.2]octane, and bipy is 4,4′-bipyridine),
were prepared via postsynthetic ligand exchanges of [Ni(HBTC)(bipy)]
(<b>1</b>). By controlling the concentration of dabco, we could
obtain not only entropically favorable <b>2</b> with completely
exchanged dabco but also enthalpically favorable <b>3</b> with
selectively exchanged bipy/dabco in the alternating layers
