Three dimensional porous Hofmann clathrate [MIIPtII(CN)4]∞ (M = Co, Ni) synthesized by using postsynthetic reductive elimination

Abstract

We synthesized cyano-bridged three dimensional metal–organic frameworks [M^II(H₂O)₂Pt^IV(CN)₄Br₂]_∞·n(H₂O) (1: M = Co, 2: M = Ni) with an NbO type topology. Although 1 and 2 have no accessible pores, these MOFs were found to undergo reductive elimination of the axial bromides on the Pt^IV ions as well as removal of water molecules upon heating to form porous [M^IIPt^II(CN)₄]_∞ (1′: M = Co, 2′: M = Ni) with retention of their crystallinity.