Solid state coordination chemistry: one-, two-, and three-dimensional materials constructed from molybdophosphonate subunits linked through binuclear copper tetra-2-pyridylpyrazine groups.
Solid state coordination chemistry: one-, two-, and three-dimensional materials constructed from molybdophosphonate subunits linked through binuclear copper tetra-2-pyridylpyrazine groups.
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DOI：
10.1021/ic030169o
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发表时间：
2003-10
影响因子：
4.6
通讯作者：
E. Burkholder;V. Golub;C. O'connor;J. Zubieta
中科院分区：
文献类型：
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作者：
E. Burkholder;V. Golub;C. O'connor;J. Zubieta
MoO（3）、适当的Cu（II）源、四-2-吡啶基吡嗪（tpypyz）、磷酸和/或有机膦酸盐的水热反应产生了一系列的铜-二磷酸盐家族的有机-无机杂化材料。这些结构的一个共同特征是作为分子构建块的化学稳定的[Mo（5）O（15）（O（3）PR）（2）]（4）（-）簇的扩展结构内的夹带。团簇是一维材料[[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）和[[Cu（2）（tpypyz）（H（2）O）]Mo（5）O（15）（O（3）PC（6）H（5））（2）].2H（2）O（2.2H（2）O），二维网络[[Cu（2）（tpypyz）（H（2）O）（3）]Mo（5）O（15）（HPO（4））（2）].2H（2）O（5.2H（2）O）和三维骨架[[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）].在亚甲基二膦酸酯作为磷组分的情况下，配体的独特螯合性质排除了五钼酸盐核的形成，生成链状结构[[Cu（2）（tpypyz）（H（2）O）]Mo（3）O（8）（HO（3）PCH（2）PO（3））（2）].8H（2）O（3.8H（2）O）和[[Cu（2）（tpypyz）（H（2）O）]（2）（Mo（3）O（8））（2）（O（3）PCH（2）PO（3））（3）].16.9H（2）O（4.16.9H（2）O）。对于结构1-7，第二金属配体结构单元是双核[Cu（2）（tpypyz）（H（2）O）（x）]（4+）簇。有相当大的结构多样性的结果，在磷钼酸盐簇，Cu（II）的配位几何形状，这可能是四，五，或六配位，水连接的程度，以及参与的磷酸氧原子，以及在键合到铜网站的alcohoxo基团的数量的变化。晶体数据：1.H（2）O，C（26）H（28）N（6）Cu（2）Mo（5）O（28）P（2），单斜晶系C2/c，a = 42.497（2）A，B = 10.7421（4）A，c = 20.5617（8）A，β = 117.178（1）度，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），单斜晶系P2（1）/c，a = 11.2478（7）A，B = 19.513（1）A，c = 21.063（1）A，β = 93.608（1）度，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），单斜晶系C2/c，a = 32.580（2）A，B = 17.8676（9）A，c = 15.9612（8）A，β = 104.430（1）度，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），单斜晶系P2（1）/c，a = 27.929（3）A，B = 12.892（2）A，c = 22.763（3）A，β = 90.367（2）度，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），单斜晶系P2（1）/n，a = 11.3222（4）A，B = 18.7673（7）A，c = 19.4124（7）A，β = 98.819（1）度，V = 4076.1（3）A（3），Z = 4; 6.2.25 H（2）O，C（27）H（28.5）N（6）Cu（2）Mo（5）O（24.25）P（2），单斜晶系C2/c，a = 12.8366（5）A，B = 18.4221（8）A，c = 34.326（1）A，β = 100.546（1）度，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），单斜晶系C2/c，a = 12.577（1）A，B = 18.336（1）A，c = 36.476（3）A，β = 91.929（2）度，V = 8407.3 A（3），Z = 8。
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)](4)(-) 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)](2)(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)](4+) 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.