Postsynthetic Exchanges of the Pillaring Ligand in Three-Dimensional Metal–Organic Frameworks

Metal–organic frameworks, [Ni­(HBTC)­(dabco)] (<b>2</b>) and [Ni₂(HBTC)₂(bipy)_0.6(dabco)_1.4] (<b>3</b>) (where H₃BTC 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