Solid state coordination chemistry of oxomolybdenum-organodiphosphonate materials: Consequences of introducing xylyldiphosphonate components

Tiffany M. Smith, Kathryn Perkins, Diona Symester, Steve R. Freund, Jose Vargas, Leonard Spinu, Jon A Zubieta

Research output: Contribution to journalArticle

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Abstract

Hydrothermal syntheses were used to prepare compounds of the oxomolybdenum/xylyldiphosphonate and oxomolybdenum/M(ii)-imine/ xylyldiphosphonate families. Four compounds exhibited unadorned molybdophosphonate chains with the common {Mo5O15(O 3PR)2}4- building unit: (4,4′-H 2dpa)2[Mo5O15(1,2-O 3PC8H8PO3)]·H2O (1·H2O), (4,4′-H2dpa)2[Mo 5O15(1,3-O3PC8H8PO 3)] (2), [Cu(terpy)2](H3O)[Mo5O 15(1,4-O3PC8H8PO3)] ·H2O (3·H2O), and [Co(2,2′-bpy) 3](H3O)[Mo5(H2O)O 14(1,4-O3PC8H8PO3)] ·6H2O (4·6H2O). The pentanuclear building unit is preserved in the one-dimensional materials [{Cu(2,2′-bpy) 2}2Mo5O15(1,4-O3PC 8H8PO3)]·6H2O (5·6H2O), [{Cu(H2O)2(o-phen)} 2Mo5O15(1,4-HO3PC8H 8PO3)]·4H2O (6·4H2O), and (4,4′-Hbpy)[Ni(H2O)4(4,4′-Hbpy)}Mo 5O15(1,2-O3PC8H8PO 3)]·4H2O (8·4H2O), while a modified, protonated pentanuclear core is observed for [{Cu(H 2O)(o-phen)}2(1,4-HO3PC8H 8PO3H)][{Cu(o-phen)(H2O)}Mo5O 14(OH)(1,4-O3PC8H8PO 3)]2 (7), a material that also exhibits two discrete one-dimensional substructures. In contrast, the one-dimensional [{Ni(H 2O)(tpypyz)}2Mo6O18(H 2O)(1,4-O3PC8H8PO 3)]·6H2O (9·6H2O) is constructed from hexanuclear molybdate clusters, and the two-dimensional [{Ni 2(H2O)4(tpypyz)}Mo4O 10(1,4-O3PC8H8PO3) 2]·4H2O (10·4H2O) exhibits a unique tetranuclear core unit. The three-dimensional phase, [{Ni(H 2O)(2,2′-dpa)}2Mo5O15(1,4- O3PC8H8PO3)]·2H2O (11·2H2O), reverts to the prototypical pentanuclear building unit. When the HF/Mo ratio of the reaction is increased from 4:1 to 8:1 or higher, three examples of oxyfluoromolybdate containing materials are observed: the one-dimensional [{Cu(o-phen)}2Mo2F5O 4(OH)(H2O)4(1,3-O3PC 8H8PO3)]·H2O (12·H2O); a structure displaying two discrete bimetallic oxyfluoride chains, [{Cu(terpy)2(OH)(H2O)}Mo 2F4O3(1,2-O3PC8H 8PO3)][{Cu(terpy)(H2O)}Mo2F 3O4(1,2-O3PC8H8PO 3)]·H2O (13·H2O); and a three dimensional compound, [{Cu3(bpy)2}Mo2F 2O4(H2O)2(1,3-O3PC 8H8PO3)2] (14). The structures of these materials are compared to those of previously described phases of the oxomolybdate/M(ii)-imine/organophosphonate and oxyfluoromolybdate/M(ii)-imine/ organophosphonate families. This journal is

Original languageEnglish (US)
Pages (from-to)191-213
Number of pages23
JournalCrystEngComm
Volume16
Issue number2
DOIs
StatePublished - Jan 14 2014

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imines
Imines
chemistry
solid state
Organophosphonates
oxyfluorides
molybdates
substructures
Hydrothermal synthesis
synthesis

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

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Solid state coordination chemistry of oxomolybdenum-organodiphosphonate materials : Consequences of introducing xylyldiphosphonate components. / Smith, Tiffany M.; Perkins, Kathryn; Symester, Diona; Freund, Steve R.; Vargas, Jose; Spinu, Leonard; Zubieta, Jon A.

In: CrystEngComm, Vol. 16, No. 2, 14.01.2014, p. 191-213.

Research output: Contribution to journalArticle

Smith, Tiffany M. ; Perkins, Kathryn ; Symester, Diona ; Freund, Steve R. ; Vargas, Jose ; Spinu, Leonard ; Zubieta, Jon A. / Solid state coordination chemistry of oxomolybdenum-organodiphosphonate materials : Consequences of introducing xylyldiphosphonate components. In: CrystEngComm. 2014 ; Vol. 16, No. 2. pp. 191-213.
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abstract = "Hydrothermal syntheses were used to prepare compounds of the oxomolybdenum/xylyldiphosphonate and oxomolybdenum/M(ii)-imine/ xylyldiphosphonate families. Four compounds exhibited unadorned molybdophosphonate chains with the common {Mo5O15(O 3PR)2}4- building unit: (4,4′-H 2dpa)2[Mo5O15(1,2-O 3PC8H8PO3)]·H2O (1·H2O), (4,4′-H2dpa)2[Mo 5O15(1,3-O3PC8H8PO 3)] (2), [Cu(terpy)2](H3O)[Mo5O 15(1,4-O3PC8H8PO3)] ·H2O (3·H2O), and [Co(2,2′-bpy) 3](H3O)[Mo5(H2O)O 14(1,4-O3PC8H8PO3)] ·6H2O (4·6H2O). The pentanuclear building unit is preserved in the one-dimensional materials [{Cu(2,2′-bpy) 2}2Mo5O15(1,4-O3PC 8H8PO3)]·6H2O (5·6H2O), [{Cu(H2O)2(o-phen)} 2Mo5O15(1,4-HO3PC8H 8PO3)]·4H2O (6·4H2O), and (4,4′-Hbpy)[Ni(H2O)4(4,4′-Hbpy)}Mo 5O15(1,2-O3PC8H8PO 3)]·4H2O (8·4H2O), while a modified, protonated pentanuclear core is observed for [{Cu(H 2O)(o-phen)}2(1,4-HO3PC8H 8PO3H)][{Cu(o-phen)(H2O)}Mo5O 14(OH)(1,4-O3PC8H8PO 3)]2 (7), a material that also exhibits two discrete one-dimensional substructures. In contrast, the one-dimensional [{Ni(H 2O)(tpypyz)}2Mo6O18(H 2O)(1,4-O3PC8H8PO 3)]·6H2O (9·6H2O) is constructed from hexanuclear molybdate clusters, and the two-dimensional [{Ni 2(H2O)4(tpypyz)}Mo4O 10(1,4-O3PC8H8PO3) 2]·4H2O (10·4H2O) exhibits a unique tetranuclear core unit. The three-dimensional phase, [{Ni(H 2O)(2,2′-dpa)}2Mo5O15(1,4- O3PC8H8PO3)]·2H2O (11·2H2O), reverts to the prototypical pentanuclear building unit. When the HF/Mo ratio of the reaction is increased from 4:1 to 8:1 or higher, three examples of oxyfluoromolybdate containing materials are observed: the one-dimensional [{Cu(o-phen)}2Mo2F5O 4(OH)(H2O)4(1,3-O3PC 8H8PO3)]·H2O (12·H2O); a structure displaying two discrete bimetallic oxyfluoride chains, [{Cu(terpy)2(OH)(H2O)}Mo 2F4O3(1,2-O3PC8H 8PO3)][{Cu(terpy)(H2O)}Mo2F 3O4(1,2-O3PC8H8PO 3)]·H2O (13·H2O); and a three dimensional compound, [{Cu3(bpy)2}Mo2F 2O4(H2O)2(1,3-O3PC 8H8PO3)2] (14). The structures of these materials are compared to those of previously described phases of the oxomolybdate/M(ii)-imine/organophosphonate and oxyfluoromolybdate/M(ii)-imine/ organophosphonate families. This journal is",
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T1 - Solid state coordination chemistry of oxomolybdenum-organodiphosphonate materials

T2 - Consequences of introducing xylyldiphosphonate components

AU - Smith, Tiffany M.

AU - Perkins, Kathryn

AU - Symester, Diona

AU - Freund, Steve R.

AU - Vargas, Jose

AU - Spinu, Leonard

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N2 - Hydrothermal syntheses were used to prepare compounds of the oxomolybdenum/xylyldiphosphonate and oxomolybdenum/M(ii)-imine/ xylyldiphosphonate families. Four compounds exhibited unadorned molybdophosphonate chains with the common {Mo5O15(O 3PR)2}4- building unit: (4,4′-H 2dpa)2[Mo5O15(1,2-O 3PC8H8PO3)]·H2O (1·H2O), (4,4′-H2dpa)2[Mo 5O15(1,3-O3PC8H8PO 3)] (2), [Cu(terpy)2](H3O)[Mo5O 15(1,4-O3PC8H8PO3)] ·H2O (3·H2O), and [Co(2,2′-bpy) 3](H3O)[Mo5(H2O)O 14(1,4-O3PC8H8PO3)] ·6H2O (4·6H2O). The pentanuclear building unit is preserved in the one-dimensional materials [{Cu(2,2′-bpy) 2}2Mo5O15(1,4-O3PC 8H8PO3)]·6H2O (5·6H2O), [{Cu(H2O)2(o-phen)} 2Mo5O15(1,4-HO3PC8H 8PO3)]·4H2O (6·4H2O), and (4,4′-Hbpy)[Ni(H2O)4(4,4′-Hbpy)}Mo 5O15(1,2-O3PC8H8PO 3)]·4H2O (8·4H2O), while a modified, protonated pentanuclear core is observed for [{Cu(H 2O)(o-phen)}2(1,4-HO3PC8H 8PO3H)][{Cu(o-phen)(H2O)}Mo5O 14(OH)(1,4-O3PC8H8PO 3)]2 (7), a material that also exhibits two discrete one-dimensional substructures. In contrast, the one-dimensional [{Ni(H 2O)(tpypyz)}2Mo6O18(H 2O)(1,4-O3PC8H8PO 3)]·6H2O (9·6H2O) is constructed from hexanuclear molybdate clusters, and the two-dimensional [{Ni 2(H2O)4(tpypyz)}Mo4O 10(1,4-O3PC8H8PO3) 2]·4H2O (10·4H2O) exhibits a unique tetranuclear core unit. The three-dimensional phase, [{Ni(H 2O)(2,2′-dpa)}2Mo5O15(1,4- O3PC8H8PO3)]·2H2O (11·2H2O), reverts to the prototypical pentanuclear building unit. When the HF/Mo ratio of the reaction is increased from 4:1 to 8:1 or higher, three examples of oxyfluoromolybdate containing materials are observed: the one-dimensional [{Cu(o-phen)}2Mo2F5O 4(OH)(H2O)4(1,3-O3PC 8H8PO3)]·H2O (12·H2O); a structure displaying two discrete bimetallic oxyfluoride chains, [{Cu(terpy)2(OH)(H2O)}Mo 2F4O3(1,2-O3PC8H 8PO3)][{Cu(terpy)(H2O)}Mo2F 3O4(1,2-O3PC8H8PO 3)]·H2O (13·H2O); and a three dimensional compound, [{Cu3(bpy)2}Mo2F 2O4(H2O)2(1,3-O3PC 8H8PO3)2] (14). The structures of these materials are compared to those of previously described phases of the oxomolybdate/M(ii)-imine/organophosphonate and oxyfluoromolybdate/M(ii)-imine/ organophosphonate families. This journal is

AB - Hydrothermal syntheses were used to prepare compounds of the oxomolybdenum/xylyldiphosphonate and oxomolybdenum/M(ii)-imine/ xylyldiphosphonate families. Four compounds exhibited unadorned molybdophosphonate chains with the common {Mo5O15(O 3PR)2}4- building unit: (4,4′-H 2dpa)2[Mo5O15(1,2-O 3PC8H8PO3)]·H2O (1·H2O), (4,4′-H2dpa)2[Mo 5O15(1,3-O3PC8H8PO 3)] (2), [Cu(terpy)2](H3O)[Mo5O 15(1,4-O3PC8H8PO3)] ·H2O (3·H2O), and [Co(2,2′-bpy) 3](H3O)[Mo5(H2O)O 14(1,4-O3PC8H8PO3)] ·6H2O (4·6H2O). The pentanuclear building unit is preserved in the one-dimensional materials [{Cu(2,2′-bpy) 2}2Mo5O15(1,4-O3PC 8H8PO3)]·6H2O (5·6H2O), [{Cu(H2O)2(o-phen)} 2Mo5O15(1,4-HO3PC8H 8PO3)]·4H2O (6·4H2O), and (4,4′-Hbpy)[Ni(H2O)4(4,4′-Hbpy)}Mo 5O15(1,2-O3PC8H8PO 3)]·4H2O (8·4H2O), while a modified, protonated pentanuclear core is observed for [{Cu(H 2O)(o-phen)}2(1,4-HO3PC8H 8PO3H)][{Cu(o-phen)(H2O)}Mo5O 14(OH)(1,4-O3PC8H8PO 3)]2 (7), a material that also exhibits two discrete one-dimensional substructures. In contrast, the one-dimensional [{Ni(H 2O)(tpypyz)}2Mo6O18(H 2O)(1,4-O3PC8H8PO 3)]·6H2O (9·6H2O) is constructed from hexanuclear molybdate clusters, and the two-dimensional [{Ni 2(H2O)4(tpypyz)}Mo4O 10(1,4-O3PC8H8PO3) 2]·4H2O (10·4H2O) exhibits a unique tetranuclear core unit. The three-dimensional phase, [{Ni(H 2O)(2,2′-dpa)}2Mo5O15(1,4- O3PC8H8PO3)]·2H2O (11·2H2O), reverts to the prototypical pentanuclear building unit. When the HF/Mo ratio of the reaction is increased from 4:1 to 8:1 or higher, three examples of oxyfluoromolybdate containing materials are observed: the one-dimensional [{Cu(o-phen)}2Mo2F5O 4(OH)(H2O)4(1,3-O3PC 8H8PO3)]·H2O (12·H2O); a structure displaying two discrete bimetallic oxyfluoride chains, [{Cu(terpy)2(OH)(H2O)}Mo 2F4O3(1,2-O3PC8H 8PO3)][{Cu(terpy)(H2O)}Mo2F 3O4(1,2-O3PC8H8PO 3)]·H2O (13·H2O); and a three dimensional compound, [{Cu3(bpy)2}Mo2F 2O4(H2O)2(1,3-O3PC 8H8PO3)2] (14). The structures of these materials are compared to those of previously described phases of the oxomolybdate/M(ii)-imine/organophosphonate and oxyfluoromolybdate/M(ii)-imine/ organophosphonate families. This journal is

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