Two new zinc-terephthalate MOFs, (H2NEt2)[Zn3(BDC)3(HCO2)]1.5DEF (1) and Zn4(BDC)3(HCO2)2(DEF)4(2), based on trinuclear zinc secondary building units have been solvothermally synthesized from the well-studied MOF-5 system Zn–H2BDC–DEF (H2BDC = 1,4-benzenedicarboxylic acid or terephthalic acid; DEF = N,N-diethylformamide). It is shown that adding small amounts of formic acid to this system has a great influence on the formation of 3D networks based upon trimetallic zinc building units Zn3(O2CR)6. The structures of 1 and 2 comprise stacked 36 tessellated 2D zinc-terephthalate layers which are linked into 3D frameworks either by bridging formate monoanions (1) or by in situ generated neutral bridging units Zn(HCO2)2(DEF)4 (2). Flowing supercritical-CO2 activation of 1 led to a partially (80%) desolvated and probably collapsed structure (1-SC) with a measured BET (Brunauer–Emmett–Teller) surface area of 38 m2 g-1

Cr-MIL-101-NH ₂ (MOF1) has been used to encapsulate large amounts of copper sulfate and the resulting loaded material, Cu@MOF1, was successfully used to promote the CuAAC click reaction.

Considering the importance of organic functionalization of MOFs, we here report a simple, tunable and efficient one-step post-modification procedure for introducing amino and carboxylic groups into the mesoporous metal–organic framework Al- and Cr-MIL-101-NH₂ based on its reaction with alkyl bromides. This procedure allows also access to polyfunctionalized MIL-101 decorated with both carboxylic and primary amino groups. Other chemical functions, such as alcohols and alkynes, were also successfully introduced by this method.

Considering the importance of organic functionalization of MOFs, we here report a simple, tunable and efficient one-step post-modification procedure for introducing amino and carboxylic groups into the mesoporous metal-organic framework Al- and Cr-MIL-101-NH2 based on its reaction with alkyl bromides. This procedure allows also access to polyfunctionnalized MIL-101 decorated with both carboxylic and primary amino groups. Other chemical functions, such as alcohols and alkynes, were also successfully introduced by this method.