Synthesis and Porous Properties of Chromium Azolate Porous Coordination Polymers

摘要

We developed a new route for synthesis of Cr-based porous coordination polymers (PCPs) with azole ligands and characterized the unique open structures by single-crystal X-ray studies and other spectroscopy techniques. Chromium-based PCPs have been prepared from azolate ligands 3,5-dimethyl-1H-pyrazole-4-carboxylic acid (H_2dmcpz) and 1,4-di(1H-tetrazole-5yl)benzene (H_2BDT) by solvothermal reactions under an Ar atmosphere. [Cr_3O(Hdmcpz)_6(DMF)_3]?DMF (1?DMF) is a coordination compound that forms a hydrogen-bonded porous network. [Cr_3O(HBDT)_2(BDT)Cl_3)]?DMF (2?DMF) possesses a new type of trinuclear chromium μ_3-O unit cluster and the novel topology of a Cr-based PCP with 700 m~2 g~(?1) of Brunauer?Emmett?Teller surface area. [Cr(BDT)(DEF)]?DEF (3?DEF) is structurally flexible and reactive to O_2 molecules because of the unsaturated Cr~(2+) centers. This is the first report of a Cr-based PCP/metal?organic framework with noncarboxylate ligands and characterization by single-crystal X-ray diffraction.