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)

Stephanie Jones, José M. Vargas, Steven Pellizzeri, Charles J. O'Connor, Jon A Zubieta

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

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.

Original languageEnglish (US)
Pages (from-to)44-57
Number of pages14
JournalInorganica Chimica Acta
Volume395
DOIs
StatePublished - Jan 30 2013

Fingerprint

Diphosphonates
Fluorides
Pyridine
fluorides
Copper
pyridines
Ligands
chemistry
solid state
Chain length
copper
ligands
Carbon
Organophosphonates
carbon
Hybrid materials
Magnetic susceptibility
Infrared spectroscopy
Metals
Single crystals

Keywords

  • Bottom-up synthesis
  • frameworks
  • Hydrothermal synthesis
  • Metal oxyfluorides
  • Molybdophosphonate building units
  • Polyoxometalate based metal organic

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

@article{5ccff97d0efd4280b24f60ca59df4df0,
title = "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)",
abstract = "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.",
keywords = "Bottom-up synthesis, frameworks, Hydrothermal synthesis, Metal oxyfluorides, Molybdophosphonate building units, Polyoxometalate based metal organic",
author = "Stephanie Jones and Vargas, {Jos{\'e} M.} and Steven Pellizzeri and O'Connor, {Charles J.} and Zubieta, {Jon A}",
year = "2013",
month = "1",
day = "30",
doi = "10.1016/j.ica.2012.10.023",
language = "English (US)",
volume = "395",
pages = "44--57",
journal = "Inorganica Chimica Acta",
issn = "0020-1693",
publisher = "Elsevier",

}

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 A

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 - frameworks

KW - Hydrothermal synthesis

KW - Metal oxyfluorides

KW - Molybdophosphonate building units

KW - Polyoxometalate based metal organic

UR - http://www.scopus.com/inward/record.url?scp=84870902291&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84870902291&partnerID=8YFLogxK

U2 - 10.1016/j.ica.2012.10.023

DO - 10.1016/j.ica.2012.10.023

M3 - Article

AN - SCOPUS:84870902291

VL - 395

SP - 44

EP - 57

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

SN - 0020-1693

ER -