Solid state coordination chemistry: Structural consequences of varying diphosphonate tether length and fluoride incorporation in he copper-bisterpy/oxomolybdenum/organodiphosphonate system (bisterpy = 2,2′:4′,4″:2″,2′″-quarterpyridyl-60, 600-di-2-pyridine)

摘要

The hydrothermal reactions of Cu(C_2H_3O _2)_2·H_2O, MoO_3, 2,2':4',4″:2″,2'″-quarterpyridyl-6',6″-di-2-pyridine (bisterpy), and organodiphosphonate ligands of varying carbon chain length in the presence of HF yield a series of novel organic-inorganic hybrid materials of the oxomolybdenum-organophosphonate family. All compounds of the study were characterized by elemental analysis, IR spectroscopy, TGA, magnetic susceptibility and single crystal X-ray diffraction. A common feature within the architectures of both the three-dimensional structure of [{Cu _2(bisterpy)(H_2O)}Mo_5O_(15){O _3P(CH_2)_4PO_3}]·4.5H _2O (1) and the one-dimensional structure of [{Cu _2(bisterpy)(H_2O)_2}Mo_5O _(15){O_3P(CH_2)_5PO_3}] (2) is the presence of {Mo_5O_(15)(O_3PR)_2} ~(4-) clusters as building blocks. In the one-dimensional [{Cu _2(bisterpy)(H_2O)_2}Mo_2F _6O_4{- HO_3P(CH_2)_4PO _3H}] (6), {Cu_2(bisterpy)}Mo_2F_4O _4{HO_3P(CH_2)_5PO_3H} _2]·2H_2O (7.2H_2O), [{Cu _2(bisterpy)(H_2-O)_2}Mo_4F _8O_8{O_3P(CH_2)_6PO _3}]·H_2O (8·H_2O) and [{Cu _2(bisterpy)(H_2O)_2}Mo_4F _8O_8{O_3P(CH_2)_9PO _3}] (9), the two-dimensional [{Cu_2(bisterpy)(OH)}Mo _2F_3O_4{O_3P(CH_2)PO _3}]·11H_2O (3·11H_2O) and [{Cu _2(bisterpy)(H_2O)_2}Mo_4F _4O_(10){O_3P(CH_2)_2PO _3}] (4), and the three-dimensional [{Cu_2(bisterpy)}Mo _4F_6O_9{O_3P(CH_2) _3PO_3}] (5), the pentamolybdate core has not been formed due to the incorporation of fluoride ions; rather a variety of {Mo xFyOz} units link the copper-bisterpy units. All structures contain the secondary metal-ligand {Cu_2(bisterpy) (H_2O)x} binuclear unit. The materials of this study demonstrate the wide structural variety available to this family of compounds by modifying both the carbon chain length of the organodiphosphonate ligand and by incorporation of fluoride within the structure.