TY - JOUR
T1 - Construction of metal-organic oxides from molybdophosphonate clusters and copper-bipyrimidine building blocks
AU - Gabriel Armatas, N.
AU - Ouellette, Wayne
AU - Whitenack, Kelly
AU - Pelcher, Joshua
AU - Liu, Hongxue
AU - Romaine, Erin
AU - O'Connor, Charles J.
AU - Zubieta, Jon
PY - 2009/9/21
Y1 - 2009/9/21
N2 - A series of organic-inorganic hybrid materials of the copper(II)- molybdophosphonate family have been prepared using conventional hydrothermal conditions. The reactions of MoO3, copper(II) acetate, bipyrimidine (bpyr), a phosphonic acid, and water at temperatures below 160 °C and in the presence of a mineralizer such as acetic acid or HF provided crystalline samples of materials of the general class {Cu2(bpyr)} 4+/MoxOy-phosphonate. The recurrent themes of the structures are the presence of the binuclear {Cu2(bpyr)} 4+ and pentanuclear (Mo5O15(O 3PR)2)4- building blocks. For the alkylphosphonate-containing materials, [{Cu2(bpyr) 2}Mo5O15(O3PCH3) 2]-2.5H2O (1 -2.5H2O) is two-dimensional and exhibits {Cu(bpyr)}.,217 chains, while [{Cu2(bpyr)(H 2O)}Mo5O15(O3PCH2CH 3)2] (2) is three-dimensional. The diphosphonate series of materials {{Cu2(bpyr)}4+[Mo5O 15{O3P(CH2)nPO3}] 4- with n = 2-6 (4,5,7-9) in all cases contain the characteristic [Mo5O15{O3P(CH2),PO 3}]n2n+ chains, linked through {Cu 2(bpyr)}4+ rods into three-dimensional frameworks. When n = 1, the threedimensional phase [{Cu2(bpyr)}MoO2(HO 3PCH2PO3)2] • 2H2O (3- 2H2O) is obtained, the exclusive example of a structure constructed from isolated {MoO8} polyhedra rather than pentamolybdate clusters. The Ni(II)-containing phase [{Ni2(bpyr)(H 2O)4}Mo5O15{O3P(CH 2)3PO3}]-9H2O (6-9H2O) was also prepared and compared to the structure of the Cu(II) analogue, [{Cu2(bpyr)(H2O)4}Mo5O 15{O3P(CH2)3PO3}]-3H 2O (5-3H2O). Magnetic susceptibility studies of the compounds revealed that the magnetic behavior was consistent in all cases with antiferromagnetically coupled dimers. However, the magnitude of the exchange coupling was clearly dependent on the orientation of the M(II) mean equatorial or basal planes relative to the bipyrimidine plane. Thus, when the metal and bipyrimidine planes are nearly coplanar, the Jvalues are in the -77 to -87 cm1 range, while J values of -2 to -5 cm1 are observed for the compounds with out-of-plane orientations.
AB - A series of organic-inorganic hybrid materials of the copper(II)- molybdophosphonate family have been prepared using conventional hydrothermal conditions. The reactions of MoO3, copper(II) acetate, bipyrimidine (bpyr), a phosphonic acid, and water at temperatures below 160 °C and in the presence of a mineralizer such as acetic acid or HF provided crystalline samples of materials of the general class {Cu2(bpyr)} 4+/MoxOy-phosphonate. The recurrent themes of the structures are the presence of the binuclear {Cu2(bpyr)} 4+ and pentanuclear (Mo5O15(O 3PR)2)4- building blocks. For the alkylphosphonate-containing materials, [{Cu2(bpyr) 2}Mo5O15(O3PCH3) 2]-2.5H2O (1 -2.5H2O) is two-dimensional and exhibits {Cu(bpyr)}.,217 chains, while [{Cu2(bpyr)(H 2O)}Mo5O15(O3PCH2CH 3)2] (2) is three-dimensional. The diphosphonate series of materials {{Cu2(bpyr)}4+[Mo5O 15{O3P(CH2)nPO3}] 4- with n = 2-6 (4,5,7-9) in all cases contain the characteristic [Mo5O15{O3P(CH2),PO 3}]n2n+ chains, linked through {Cu 2(bpyr)}4+ rods into three-dimensional frameworks. When n = 1, the threedimensional phase [{Cu2(bpyr)}MoO2(HO 3PCH2PO3)2] • 2H2O (3- 2H2O) is obtained, the exclusive example of a structure constructed from isolated {MoO8} polyhedra rather than pentamolybdate clusters. The Ni(II)-containing phase [{Ni2(bpyr)(H 2O)4}Mo5O15{O3P(CH 2)3PO3}]-9H2O (6-9H2O) was also prepared and compared to the structure of the Cu(II) analogue, [{Cu2(bpyr)(H2O)4}Mo5O 15{O3P(CH2)3PO3}]-3H 2O (5-3H2O). Magnetic susceptibility studies of the compounds revealed that the magnetic behavior was consistent in all cases with antiferromagnetically coupled dimers. However, the magnitude of the exchange coupling was clearly dependent on the orientation of the M(II) mean equatorial or basal planes relative to the bipyrimidine plane. Thus, when the metal and bipyrimidine planes are nearly coplanar, the Jvalues are in the -77 to -87 cm1 range, while J values of -2 to -5 cm1 are observed for the compounds with out-of-plane orientations.
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U2 - 10.1021/ic901133k
DO - 10.1021/ic901133k
M3 - Article
C2 - 19685900
AN - SCOPUS:70349311564
SN - 0020-1669
VL - 48
SP - 8897
EP - 8910
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 18
ER -