Functionalization of robust Zr(IV)-based metal-organic framework films via a postsynthetic ligand exchange.

A facile and efficient fabrication approach for homogeneous, crack-free UiO-66 films with exceptionally high crystallinity and tunable thickness on a transparent and conductive glass substrate is reported. Two functionalized species, a catechol ligand and a Fe2 complex with structural resemblance to the active site of [FeFe] hydrogenase, were introduced into the MOF films via a postsynthetic exchange. Voltammetric studies show the [FeFe] complex in the thinner UiO-66 films (2-5 μm) can be reduced electrochemically.