TY - JOUR
T1 - Solid state coordination chemistry
T2 - 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)
AU - Jones, Stephanie
AU - Vargas, José M.
AU - Pellizzeri, Steven
AU - O'Connor, Charles J.
AU - Zubieta, Jon
N1 - Funding Information:
This work was supported by a grant from the National Science Foundation , CHE-0242153 .
PY - 2013/1/30
Y1 - 2013/1/30
N2 - The hydrothermal reactions of Cu(C2H3O 2)2·H2O, MoO3, 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)(H2O)}Mo5O15{O 3P(CH2)4PO3}]·4.5H 2O (1) and the one-dimensional structure of [{Cu 2(bisterpy)(H2O)2}Mo5O 15{O3P(CH2)5PO3}] (2) is the presence of {Mo5O15(O3PR)2} 4- clusters as building blocks. In the one-dimensional [{Cu 2(bisterpy)(H2O)2}Mo2F 6O4{- HO3P(CH2)4PO 3H}] (6), {Cu2(bisterpy)}Mo2F4O 4{HO3P(CH2)5PO3H} 2]·2H2O (7.2H2O), [{Cu 2(bisterpy)(H2-O)2}Mo4F 8O8{O3P(CH2)6PO 3}]·H2O (8·H2O) and [{Cu 2(bisterpy)(H2O)2}Mo4F 8O8{O3P(CH2)9PO 3}] (9), the two-dimensional [{Cu2(bisterpy)(OH)}Mo 2F3O4{O3P(CH2)PO 3}]·11H2O (3·11H2O) and [{Cu 2(bisterpy)(H2O)2}Mo4F 4O10{O3P(CH2)2PO 3}] (4), and the three-dimensional [{Cu2(bisterpy)}Mo 4F6O9{O3P(CH2) 3PO3}] (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 {Cu2(bisterpy) (H2O)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.
AB - The hydrothermal reactions of Cu(C2H3O 2)2·H2O, MoO3, 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)(H2O)}Mo5O15{O 3P(CH2)4PO3}]·4.5H 2O (1) and the one-dimensional structure of [{Cu 2(bisterpy)(H2O)2}Mo5O 15{O3P(CH2)5PO3}] (2) is the presence of {Mo5O15(O3PR)2} 4- clusters as building blocks. In the one-dimensional [{Cu 2(bisterpy)(H2O)2}Mo2F 6O4{- HO3P(CH2)4PO 3H}] (6), {Cu2(bisterpy)}Mo2F4O 4{HO3P(CH2)5PO3H} 2]·2H2O (7.2H2O), [{Cu 2(bisterpy)(H2-O)2}Mo4F 8O8{O3P(CH2)6PO 3}]·H2O (8·H2O) and [{Cu 2(bisterpy)(H2O)2}Mo4F 8O8{O3P(CH2)9PO 3}] (9), the two-dimensional [{Cu2(bisterpy)(OH)}Mo 2F3O4{O3P(CH2)PO 3}]·11H2O (3·11H2O) and [{Cu 2(bisterpy)(H2O)2}Mo4F 4O10{O3P(CH2)2PO 3}] (4), and the three-dimensional [{Cu2(bisterpy)}Mo 4F6O9{O3P(CH2) 3PO3}] (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 {Cu2(bisterpy) (H2O)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.
KW - Bottom-up synthesis
KW - Hydrothermal synthesis
KW - Metal oxyfluorides
KW - Molybdophosphonate building units
KW - Polyoxometalate based metal organic
KW - frameworks
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U2 - 10.1016/j.ica.2012.10.023
DO - 10.1016/j.ica.2012.10.023
M3 - Article
AN - SCOPUS:84870902291
SN - 0020-1693
VL - 395
SP - 44
EP - 57
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
ER -