Post-synthetic modification of Isomorphic coordination polymers with metal ion exchange and catalytic cycloaddition of CO2.

A coordination polymeric crystal 1 was successfully synthesized from H 4 L (5,5′-(1,4-phenylenebis (methoxy))diisophthalic acid), bidpe (4,4′-bis(lmidazolyl)diphenyl ether), and Zn(NO 3) 2 ·6H 2 O under solvothermal conditions, and characterized by single-crystal X-ray diffraction. Then, two new crystals 1 Fe and 1 Cu were obtained with metal ion exchange when 1 was dipped into the DMF solution for FeCl 2 and CuCl 2 , respectively. The exchange process demonstrated that the high valence metal ion with strong acidity could be destroyed the structure of the crystals. Therefore, it should be exchanged with lower valence ion and then oxidized to the high valence state, which could be a feasible way to obtain the crystals with high valence metal ions. Further, the magnetic property and the synergistic CO 2 conversion with epoxide for 1 Fe and 1 Cu were also investigated, and the results shown that 1 Fe could be regarded as a potential catalyst for this conversion. Three two dimensional two-fold interpenetrated MOFs 1 , 1 Fe and 1 Cu were successfully synthesized via solvothermal or post-synthetic modification. 1 Fe and 1 Cu shown excellent abilities for catalyzed cycloaddition of CO 2 to epoxides. [Display omitted] 1. Three novel dimensional MOFs 1 , 1 Fe and 1 Cu , have been synthesized via solvent-thermal treatment and post-synthetic exchange approach. 2. Zn(II) ions were exchange with Fe(III) ions in 1 Fe. But, due to the strong acidity of Fe(III) ions could destroy the crystal framework, the exchange only could be happen when 1 was dipped into the freshly FeCl 2 -DMF solution. 3. Variable-temperature magnetic studies indicate that 1 Fe contains the weak ferromagnetic chain while 1 Cu contains the weak antiferromagnetic (AF) interactions. 4. The catalytic properties of 1 , 1 Fe and 1 Cu for epoxides' cycloaddition reactions with CO 2 , and the results shown that 1 Fe and 1 Cu could be good catalysts for this reaction. [ABSTRACT FROM AUTHOR]