Reprogramming Kinetic Phase Control and Tailoring Pore Environments in CoII and ZnII Metal–Organic Frameworks

摘要: Metal–organic frameworks (MOFs) 1-Co and 1-Zn ([M3(L)(H2L)(DMF)(DABCO)], where M = Co Zn), which are based on trimeric nodal clusters (MTdMOhMTd), have been synthesized from the ligands 2,2′-dihydroxy-1,1′-biphenyl-4,4′-dicarboxylic acid (H4L) 1,4-diazabicyclo[2.2.2]octane (DABCO). High temperature synthesis (150 °C) led to formation of 1-Co, but an identical reaction mixture gave exclusively 2-Co ([Co(H2L)(DMF)2]) when reacted at 65 °C. Reactions intermediate temperatures a products confirming that is thermodynamic product kinetic product. Conditions used form °C were “reprogrammed” by doping solution with ZnII generate thermodynamically favored phase (1-M) mixed CoII/ZnII composition, 1-CoZn. Heterometallic mixtures ZnII/CoII explored for range starting metal ratios, showing preferential incorporation CoII over 150 Furthermore, coordination ions free diol moieties i...