Abstract
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 38m2g−1.
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