TY - JOUR
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
AU - Zubieta, Jon
PY - 2014/1/14
Y1 - 2014/1/14
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.
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.
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U2 - 10.1039/c3ce41728j
DO - 10.1039/c3ce41728j
M3 - Article
AN - SCOPUS:84890064156
SN - 1466-8033
VL - 16
SP - 191
EP - 213
JO - CrystEngComm
JF - CrystEngComm
IS - 2
ER -