固态配位化学：由通过双核四-2-吡啶基吡嗪铜基团连接的钼膦酸盐亚基构建的一维、二维和三维材料。
Solid state coordination chemistry: one-, two-, and three-dimensional materials constructed from molybdophosphonate subunits linked through binuclear copper tetra-2-pyridylpyrazine groups.
作者信息
Burkholder Eric, Golub Vladimir, O'Connor Charles J, Zubieta Jon
机构信息
Department of Chemistry, Syracuse University, Syracuse, New York 13244, USA.
出版信息
Inorg Chem. 2003 Oct 20;42(21):6729-40. doi: 10.1021/ic030169o.
The hydrothermal reactions of MoO(3), an appropriate Cu(II) source, tetra-2-pyridylpyrazine (tpypyz), and phosphoric acid and/or an organophosphonate yielded a series of organic-inorganic hybrid materials of the copper-molybdophosphonate family. A common feature of the structures is the entrainment within the extended architectures of chemically robust Mo(5)O(15)(O(3)PR)(2)(-) clusters as molecular building blocks. The cluster is a characteristic feature of the one-dimensional materials [[Cu(2)(tpypyz)(H(2)O)(3)]Mo(5)O(15)(HPO(4))(O(3)PCH(2)CO(2)H)].H(2)O (1.H(2)O) and [[Cu(2)(tpypyz)(H(2)O)]Mo(5)O(15)(O(3)PC(6)H(5))(2)].2H(2)O (2.2H(2)O), the two-dimensional network [[Cu(2)(tpypyz)(H(2)O)(3)]Mo(5)O(15)(HPO(4))(2)].2H(2)O (5.2H(2)O) and the three-dimensional frameworks [[Cu(2)(tpypyz)(H(2)O)(2)]Mo(5)O(15)[O(3)P(CH(2))(n)()PO(3)]].xH(2)O [n = 3, x = 2.25 (6.2.25H(2)O); n = 4, x = 0.33 (7.0.33H(2)O)]. In the case of methylenediphosphonate as the phosphorus component, the unique chelating nature of the ligand precludes formation of the pentamolybdate core, resulting in the chain structures [[Cu(2)(tpypyz)(H(2)O)]Mo(3)O(8) (HO(3)PCH(2)PO(3))(2)].8H(2)O (3.8H(2)O) and [Cu(2)(tpypyz)(H(2)O)(Mo(3)O(8))(2)(O(3)PCH(2)PO(3))(3)].16.9H(2)O (4.16.9H(2)O). For structures 1-7, the secondary metal-ligand building block is the binuclear Cu(2)(tpypyz)(H(2)O)(x) cluster. There is considerable structural versatility as a result of the variability in the number of attachment sites at the phosphomolybdate clusters, the coordination geometry of the Cu(II), which may be four-, five-, or six-coordinate, the extent of aqua ligation, and the participation of phosphate oxygen atoms as well as molybdate oxo groups in bonding to the copper sites. Crystal data: 1.H(2)O, C(26)H(28)N(6)Cu(2)Mo(5)O(28)P(2), monoclinic C2/c, a = 42.497(2) A, b = 10.7421(4) A, c = 20.5617(8) A, beta = 117.178(1) degrees, V = 8350.1(5) A(3), Z = 8; 2.2H(2)O, C(36)H(32)N(6)Cu(2)Mo(5)O(24)P(2), monoclinic P2(1)/c, a = 11.2478(7) A, b = 19.513(1) A, c = 21.063(1) A, beta = 93.608(1) degrees, V = 4613.7(5) A(3), Z = 4; 3.8H(2)O, C(26)H(40)N(6)Cu(2)Mo(3)O(29)P(4), monoclinic C2/c, a = 32.580(2) A, b = 17.8676(9) A, c = 15.9612(8) A, beta = 104.430(1) degrees, V = 8993.3(8) A(3), Z = 8; 4.16.9H(2)O, C(51)H(71.75)Cu(4)Mo(6)N(12)O(51)P(6), monoclinic P2(1)/c, a = 27.929(3) A, b = 12.892(2) A, c = 22.763(3) A, beta = 90.367(2) degrees, V = 8195.7(2) A(3), Z = 4;( )()5.2H(2)O, C(24)H(28)N(6)Cu(2)Mo(5)O(28)P(2), monoclinic P2(1)/n, a = 11.3222(4) A, b = 18.7673(7) A, c = 19.4124(7) A, beta = 98.819(1) degrees, V = 4076.1(3) A(3), Z = 4; 6.2.25H(2)O, C(27)H(28.5)N(6)Cu(2)Mo(5)O(24.25)P(2), monoclinic C2/c, a = 12.8366(5) A, b = 18.4221(8) A, c = 34.326(1) A, beta = 100.546(1) degrees, V = 7980.1(6) A(3), Z = 8; 7.(1)/(3)H(2)O, C(28)H(28.7)N(6)Cu(2)Mo(5)O(23.3)P(2), monoclinic C2/c, a = 12.577(1) A, b = 18.336(1) A, c = 36.476(3) A, beta = 91.929(2) degrees, V = 8407.3 A(3), Z = 8.
三氧化钼、合适的铜（II）源、四-2-吡啶基吡嗪（tpypyz）以及磷酸和/或有机膦酸盐的水热反应生成了一系列铜-钼膦酸盐家族的有机-无机杂化材料。这些结构的一个共同特征是，在扩展结构中包含化学性质稳定的[Mo₅O₁₅(O₃PR)₂]⁴⁻簇作为分子构建块。该簇是一维材料[[Cu₂(tpypyz)(H₂O)₃]Mo₅O₁₅(HPO₄)(O₃PCH₂CO₂H)].H₂O (1.H₂O) 和 [[Cu₂(tpypyz)(H₂O)]Mo₅O₁₅(O₃PC₆H₅)₂].2H₂O (2.2H₂O)、二维网络[[Cu₂(tpypyz)(H₂O)₃]Mo₅O₁₅(HPO₄)₂].2H₂O (5.2H₂O) 以及三维骨架[[Cu₂(tpypyz)(H₂O)₂]Mo₅O₁₅[O₃P(CH₂)ₙPO₃]].xH₂O [n = 3, x = 2.25 (6.2.25H₂O); n = 4, x = 0.33 (7.0.33H₂O)] 的特征。在以亚甲基二膦酸盐作为磷组分的情况下，配体独特的螯合性质阻止了五钼酸盐核心的形成，从而形成链状结构[[Cu₂(tpypyz)(H₂O)]Mo₃O₈(HO₃PCH₂PO₃)₂].8H₂O (3.8H₂O) 和 [[Cu₂(tpypyz)(H₂O)]₂(Mo₃O₈)₂(O₃PCH₂PO₃)₃].16.9H₂O (4.16.9H₂O)。对于结构1 - 7，二级金属-配体构建块是双核[Cu₂(tpypyz)(H₂O)ₓ]⁴⁺簇。由于磷钼酸盐簇上连接位点数量的变化、铜（II）的配位几何结构（可能为四配位、五配位或六配位）、水配位的程度以及磷酸氧原子和钼酸氧基团参与与铜位点的键合，导致了相当大的结构多样性。晶体数据：1.H₂O，C₂₆H₂₈N₆Cu₂Mo₅O₂₈P₂，单斜晶系C2/c，a = 42.497(2) Å，b = 10.7421(4) Å，c = 20.5617(8) Å，β = 117.178(1)°，V = 8350.1(5) ų，Z = 8；2.2H₂O，C₃₆H₃₂N₆Cu₂Mo₅O₂₄P₂，单斜晶系P2₁/c，a = 11.2478(7) Å，b = 19.513(1) Å，c = 21.063(1) Å，β = 93.608(1)°，V = 4613.7(5) ų，Z = 4；3.8H₂O，C₂₆H₄₀N₆Cu₂Mo₃O₂₉P₄，单斜晶系C2/c，a = 32.580(2) Å，b = 17.8676(9) Å，c = 15.9612(8) Å，β = 104.430(1)°，V = 8993.3(8) ų，Z = 8；4.16.9H₂O，C₅₁H₇₁.₇₅Cu₄Mo₆N₁₂O₅₁P₆，单斜晶系P2₁/c，a = 27.929(3) Å，b = 12.892(2) Å，c = 22.763(3) Å，β = 90.367(2)°，V = 8195.7(2) ų，Z = 4；5.2H₂O，C₂₄H₂₈N₆Cu₂Mo₅O₂₈P₂，单斜晶系P2₁/n，a = 11.3222(4) Å，b = 18.7673(7) Å，c = 19.4124(7) Å，β = 98.819(1)°，V = 4076.1(3) ų，Z = 4；6.2.25H₂O，C₂₇H₂₈.₅N₆Cu₂Mo₅O₂₄.₂₅P₂，单斜晶系C2/c，a = 12.8366(5) Å，b = 18.4221(8) Å，c = 34.
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