Armatas N Gabriel, Ouellette Wayne, Whitenack Kelly, Pelcher Joshua, Liu Hongxue, Romaine Erin, O'Connor Charles J, Zubieta Jon
Department of Chemistry, Syracuse University, Syracuse, New York 13244, USA.
Inorg Chem. 2009 Sep 21;48(18):8897-910. doi: 10.1021/ic901133k.
A series of organic-inorganic hybrid materials of the copper(II)-molybdophosphonate family have been prepared using conventional hydrothermal conditions. The reactions of MoO(3), copper(II) acetate, bipyrimidine (bpyr), a phosphonic acid, and water at temperatures below 160 degrees C and in the presence of a mineralizer such as acetic acid or HF provided crystalline samples of materials of the general class {Cu(2)(bpyr)}(4+)/Mo(x)O(y)-phosphonate. The recurrent themes of the structures are the presence of the binuclear {Cu(2)(bpyr)}(4+) and pentanuclear {Mo(5)O(15)(O(3)PR)(2)}(4-) building blocks. For the alkylphosphonate-containing materials, [{Cu(2)(bpyr)(2)}Mo(5)O(15)(O(3)PCH(3))(2)].2.5H(2)O (1.2.5H(2)O) is two-dimensional and exhibits {Cu(bpyr)}(n)(2n+) chains, while [{Cu(2)(bpyr)(H(2)O)}Mo(5)O(15)(O(3)PCH(2)CH(3))(2)] (2) is three-dimensional. The diphosphonate series of materials {{Cu(2)(bpyr)}(4+)Mo(5)O(15){O(3)P(CH(2))(n)PO(3)} with n = 2-6 (4, 5, 7-9) in all cases contain the characteristic Mo(5)O(15){O(3)P(CH(2))(n)PO(3)}(2n+) chains, linked through {Cu(2)(bpyr)}(4+) rods into three-dimensional frameworks. When n = 1, the three-dimensional phase [{Cu(2)(bpyr)}MoO(2)(HO(3)PCH(2)PO(3))(2)].2H(2)O (3.2H(2)O) is obtained, the exclusive example of a structure constructed from isolated {MoO(6)} polyhedra rather than pentamolybdate clusters. The Ni(II)-containing phase [{Ni(2)(bpyr)(H(2)O)(4)}Mo(5)O(15){O(3)P(CH(2))(3)PO(3)}].9H(2)O (6.9H(2)O) was also prepared and compared to the structure of the Cu(II) analogue, [{Cu(2)(bpyr)(H(2)O)(4)}Mo(5)O(15){O(3)P(CH(2))(3)PO(3)}].3H(2)O (5.3H(2)O). 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 J values are in the -77 to -87 cm(-1) range, while J values of -2 to -5 cm(-1) are observed for the compounds with out-of-plane orientations.
采用传统水热条件制备了一系列铜（II）-钼膦酸盐家族的有机-无机杂化材料。在低于160℃的温度下，在诸如乙酸或氢氟酸等矿化剂存在的情况下，三氧化钼、乙酸铜（II）、联嘧啶（bpyr）、一种膦酸和水之间的反应生成了通式为{Cu₂(bpyr)}⁴⁺/MoₓOᵧ-膦酸盐的晶体材料样品。这些结构的共同特点是存在双核{Cu₂(bpyr)}⁴⁺和五核{Mo₅O₁₅(O₃PR)₂}⁴⁻结构单元。对于含烷基膦酸盐的材料，[{Cu₂(bpyr)₂}Mo₅O₁₅(O₃PCH₃)₂]·2.5H₂O（1·2.5H₂O）是二维的，呈现出{Cu(bpyr)}ₙ²⁺ⁿ链，而[{Cu₂(bpyr)(H₂O)}Mo₅O₁₅(O₃PCH₂CH₃)₂]（2）是三维的。二膦酸盐系列材料{{Cu₂(bpyr)}⁴⁺[Mo₅O₁₅{O₃P(CH₂)ₙPO₃}]⁴⁻，其中n = 2 - 6（4, 5, 7 - 9），在所有情况下都包含特征性的[Mo₅O₁₅{O₃P(CH₂)ₙPO₃}]ⁿ²⁺ⁿ链，通过{Cu₂(bpyr)}⁴⁺棒连接成三维骨架。当n = 1时，得到三维相[{Cu₂(bpyr)}MoO₂(HO₃PCH₂PO₃)₂]·2H₂O（3·2H₂O），这是由孤立的{MoO₆}多面体而非五钼酸盐簇构建结构的唯一例子。还制备了含镍（II）相[{Ni₂(bpyr)(H₂O)₄}Mo₅O₁₅{O₃P(CH₂)₃PO₃}]·9H₂O（6·第九H₂O）并与铜（II）类似物[{Cu₂(bpyr)(H₂O)₄}Mo₅O₁₅{O₃P(CH₂)₃PO₃}]·3H₂O（5·3H₂O）的结构进行了比较。对这些化合物的磁化率研究表明，在所有情况下，磁行为都与反铁磁耦合二聚体一致。然而，交换耦合强度明显取决于M（II）平均赤道面或基面相对于联嘧啶平面的取向。因此，当金属平面和联嘧啶平面几乎共面时，J值在-77至-87 cm⁻¹范围内，而对于平面外取向的化合物，观察到的J值为-2至-5 cm⁻¹。
