Novel building units in the construction of materials of the oxomolybdate-organodiphosphonate/copper(II)-dipodal-organonitrogen ligand system: Structural influences of dipodal ligand tether length and flexibility

Mark Bartholomä, Hoi Chueng, Steven Pellizzeri, Kenneth Ellis-Guardiola, Stephanie Jones, Jon A Zubieta

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

The hydrothermal reactions of copper(II) acetate, MoO 3, 1,4-butylenediphosphonic acid and a ligand of the N,N,N′,N′- tetrakis(pyridine-2-ylmethyl)alkyl-α,ω-diamine (Ln, where n is the number of methylene groups) in the presence of HF provided crystals of [{Cu 2(L7)(H 2O) 2}Mo 5O 15{O 3P(CH 2) 4PO 3}]·2H 2O (1·2H 2O) and [{Cu 2(L5)}Mo 6O 18(H 2O){O 3P(CH 2) 4PO 3}]·14H 2O (2·14H 2O). Compound 1 contains the common pentanuclear cluster building block {Mo 5O 15(O 3PR) 2} 4-, extending into one-dimensional chains through the alkyl tethers of the diphosphonate ligand. Each pentanuclear subunit bonds to four copper(II) sites of the {Cu 2(L7)(H 2O 2)} 4+ subunits that serve to link each chain to five adjacent chains to propagate the structure in three dimensions. The Cu/Mo/P/O inorganic substructure which arises from this juxtaposition of building motifs is a one-dimensional {Cu 2Mo 5O 15(O 3P-) 2} unit consisting of clusters linked through Cu(II) sites. The alkyl arms of the diphosphonate and nitrogen ligands radiate outward to link to adjacent chains and propagate the structure in three-dimensions. In contrast, compound 2 exhibits a hexanuclear building unit {Mo 6O 18(H 2O)(O 3P-) 2} 4-, which again extends into a chain through the tethering diphosphonate ligands. Each cluster bonds to four Cu(II) centers to generate one-dimensional inorganic substructures of the type {Cu 2Mo 6O 18(H 2O)(O 3P-) 2} n. In contrast to 1, the {Cu 2(L5)} 4+ subunits of 2 associate with a single chain, rather than radiating outward to link to adjacent chains. Consequently, the three-dimensional expansion is effected through the diphosphonate tethers.

Original languageEnglish (US)
Pages (from-to)90-98
Number of pages9
JournalInorganica Chimica Acta
Volume389
DOIs
StatePublished - Jul 1 2012

Fingerprint

Diphosphonates
Copper
flexibility
Ligands
copper
ligands
Diamines
substructures
Pyridine
methylidyne
Nitrogen
tethering
Crystals
Acids
diamines
methylene
acetates
pyridines
nitrogen
acids

Keywords

  • Bimetallic oxide
  • Copper-molybdophosphonate materials
  • Hexamolybdate clusters
  • Organic-inorganic hybrid materials
  • Pentamolybdate clusters

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Novel building units in the construction of materials of the oxomolybdate-organodiphosphonate/copper(II)-dipodal-organonitrogen ligand system : Structural influences of dipodal ligand tether length and flexibility. / Bartholomä, Mark; Chueng, Hoi; Pellizzeri, Steven; Ellis-Guardiola, Kenneth; Jones, Stephanie; Zubieta, Jon A.

In: Inorganica Chimica Acta, Vol. 389, 01.07.2012, p. 90-98.

Research output: Contribution to journalArticle

@article{6e367d22b60e41e6953189dcd5c886c2,
title = "Novel building units in the construction of materials of the oxomolybdate-organodiphosphonate/copper(II)-dipodal-organonitrogen ligand system: Structural influences of dipodal ligand tether length and flexibility",
abstract = "The hydrothermal reactions of copper(II) acetate, MoO 3, 1,4-butylenediphosphonic acid and a ligand of the N,N,N′,N′- tetrakis(pyridine-2-ylmethyl)alkyl-α,ω-diamine (Ln, where n is the number of methylene groups) in the presence of HF provided crystals of [{Cu 2(L7)(H 2O) 2}Mo 5O 15{O 3P(CH 2) 4PO 3}]·2H 2O (1·2H 2O) and [{Cu 2(L5)}Mo 6O 18(H 2O){O 3P(CH 2) 4PO 3}]·14H 2O (2·14H 2O). Compound 1 contains the common pentanuclear cluster building block {Mo 5O 15(O 3PR) 2} 4-, extending into one-dimensional chains through the alkyl tethers of the diphosphonate ligand. Each pentanuclear subunit bonds to four copper(II) sites of the {Cu 2(L7)(H 2O 2)} 4+ subunits that serve to link each chain to five adjacent chains to propagate the structure in three dimensions. The Cu/Mo/P/O inorganic substructure which arises from this juxtaposition of building motifs is a one-dimensional {Cu 2Mo 5O 15(O 3P-) 2} unit consisting of clusters linked through Cu(II) sites. The alkyl arms of the diphosphonate and nitrogen ligands radiate outward to link to adjacent chains and propagate the structure in three-dimensions. In contrast, compound 2 exhibits a hexanuclear building unit {Mo 6O 18(H 2O)(O 3P-) 2} 4-, which again extends into a chain through the tethering diphosphonate ligands. Each cluster bonds to four Cu(II) centers to generate one-dimensional inorganic substructures of the type {Cu 2Mo 6O 18(H 2O)(O 3P-) 2} n. In contrast to 1, the {Cu 2(L5)} 4+ subunits of 2 associate with a single chain, rather than radiating outward to link to adjacent chains. Consequently, the three-dimensional expansion is effected through the diphosphonate tethers.",
keywords = "Bimetallic oxide, Copper-molybdophosphonate materials, Hexamolybdate clusters, Organic-inorganic hybrid materials, Pentamolybdate clusters",
author = "Mark Bartholom{\"a} and Hoi Chueng and Steven Pellizzeri and Kenneth Ellis-Guardiola and Stephanie Jones and Zubieta, {Jon A}",
year = "2012",
month = "7",
day = "1",
doi = "10.1016/j.ica.2012.01.011",
language = "English (US)",
volume = "389",
pages = "90--98",
journal = "Inorganica Chimica Acta",
issn = "0020-1693",
publisher = "Elsevier",

}

TY - JOUR

T1 - Novel building units in the construction of materials of the oxomolybdate-organodiphosphonate/copper(II)-dipodal-organonitrogen ligand system

T2 - Structural influences of dipodal ligand tether length and flexibility

AU - Bartholomä, Mark

AU - Chueng, Hoi

AU - Pellizzeri, Steven

AU - Ellis-Guardiola, Kenneth

AU - Jones, Stephanie

AU - Zubieta, Jon A

PY - 2012/7/1

Y1 - 2012/7/1

N2 - The hydrothermal reactions of copper(II) acetate, MoO 3, 1,4-butylenediphosphonic acid and a ligand of the N,N,N′,N′- tetrakis(pyridine-2-ylmethyl)alkyl-α,ω-diamine (Ln, where n is the number of methylene groups) in the presence of HF provided crystals of [{Cu 2(L7)(H 2O) 2}Mo 5O 15{O 3P(CH 2) 4PO 3}]·2H 2O (1·2H 2O) and [{Cu 2(L5)}Mo 6O 18(H 2O){O 3P(CH 2) 4PO 3}]·14H 2O (2·14H 2O). Compound 1 contains the common pentanuclear cluster building block {Mo 5O 15(O 3PR) 2} 4-, extending into one-dimensional chains through the alkyl tethers of the diphosphonate ligand. Each pentanuclear subunit bonds to four copper(II) sites of the {Cu 2(L7)(H 2O 2)} 4+ subunits that serve to link each chain to five adjacent chains to propagate the structure in three dimensions. The Cu/Mo/P/O inorganic substructure which arises from this juxtaposition of building motifs is a one-dimensional {Cu 2Mo 5O 15(O 3P-) 2} unit consisting of clusters linked through Cu(II) sites. The alkyl arms of the diphosphonate and nitrogen ligands radiate outward to link to adjacent chains and propagate the structure in three-dimensions. In contrast, compound 2 exhibits a hexanuclear building unit {Mo 6O 18(H 2O)(O 3P-) 2} 4-, which again extends into a chain through the tethering diphosphonate ligands. Each cluster bonds to four Cu(II) centers to generate one-dimensional inorganic substructures of the type {Cu 2Mo 6O 18(H 2O)(O 3P-) 2} n. In contrast to 1, the {Cu 2(L5)} 4+ subunits of 2 associate with a single chain, rather than radiating outward to link to adjacent chains. Consequently, the three-dimensional expansion is effected through the diphosphonate tethers.

AB - The hydrothermal reactions of copper(II) acetate, MoO 3, 1,4-butylenediphosphonic acid and a ligand of the N,N,N′,N′- tetrakis(pyridine-2-ylmethyl)alkyl-α,ω-diamine (Ln, where n is the number of methylene groups) in the presence of HF provided crystals of [{Cu 2(L7)(H 2O) 2}Mo 5O 15{O 3P(CH 2) 4PO 3}]·2H 2O (1·2H 2O) and [{Cu 2(L5)}Mo 6O 18(H 2O){O 3P(CH 2) 4PO 3}]·14H 2O (2·14H 2O). Compound 1 contains the common pentanuclear cluster building block {Mo 5O 15(O 3PR) 2} 4-, extending into one-dimensional chains through the alkyl tethers of the diphosphonate ligand. Each pentanuclear subunit bonds to four copper(II) sites of the {Cu 2(L7)(H 2O 2)} 4+ subunits that serve to link each chain to five adjacent chains to propagate the structure in three dimensions. The Cu/Mo/P/O inorganic substructure which arises from this juxtaposition of building motifs is a one-dimensional {Cu 2Mo 5O 15(O 3P-) 2} unit consisting of clusters linked through Cu(II) sites. The alkyl arms of the diphosphonate and nitrogen ligands radiate outward to link to adjacent chains and propagate the structure in three-dimensions. In contrast, compound 2 exhibits a hexanuclear building unit {Mo 6O 18(H 2O)(O 3P-) 2} 4-, which again extends into a chain through the tethering diphosphonate ligands. Each cluster bonds to four Cu(II) centers to generate one-dimensional inorganic substructures of the type {Cu 2Mo 6O 18(H 2O)(O 3P-) 2} n. In contrast to 1, the {Cu 2(L5)} 4+ subunits of 2 associate with a single chain, rather than radiating outward to link to adjacent chains. Consequently, the three-dimensional expansion is effected through the diphosphonate tethers.

KW - Bimetallic oxide

KW - Copper-molybdophosphonate materials

KW - Hexamolybdate clusters

KW - Organic-inorganic hybrid materials

KW - Pentamolybdate clusters

UR - http://www.scopus.com/inward/record.url?scp=84861626287&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84861626287&partnerID=8YFLogxK

U2 - 10.1016/j.ica.2012.01.011

DO - 10.1016/j.ica.2012.01.011

M3 - Article

AN - SCOPUS:84861626287

VL - 389

SP - 90

EP - 98

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

SN - 0020-1693

ER -