Cation dependent formation of hybrid organic-inorganic frameworks based on the strandberg-type polyanion [(O2CCH2PO3)2Mo5O15]6- and Cu2+ ions

被引:14
作者
Chubarova, Elena V. [1 ]
Kloeck, Cornelius [1 ]
Dickman, Michael H. [1 ]
Kortz, Ulrich [1 ]
机构
[1] Jacob Univ Bremen, Sch Sci & Engn, Bremen, Germany
关键词
polyoxomolybdates; hybrid organic-inorganic materials; phosphonocarboxylates; crystal growth; X-ray diffraction; STATE COORDINATION CHEMISTRY; MULTICOMPONENT POLYANIONS; CRYSTAL-STRUCTURE; STRUCTURAL-CHARACTERIZATION; HYDROTHERMAL SYNTHESIS; POLYMERS; CLUSTERS; SYSTEM; OXIDE; TETRA-2-PYRIDYLPYRAZINE;
D O I
10.1007/s10876-007-0128-7
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
We present the first examples of materials based on the Strandberg type polyanion [(O2CCH2PO3)(2)Mo5O15](6-), linked by Cu2+ centers via coordination to the carboxylate functions of the polyanion. Simple one-pot reaction of Rb4KNa[(O2CCH2PO3)(2)Mo5O15]center dot H2O with CuCl2 center dot 2H(2)O in aqueous acidic media followed by crystallization resulted in the three hybrid organic-inorganic materials {K2.6Rb1.4[(PO3CH2CO2)(2)Mo5O15Cu(H2O)(3)]center dot 7H(2)O} (n) (KRb-1), {Na2Cs3[(PO3CH2CO2)(2)Mo5O15(Cu(H2O)(2)Cl)]center dot 6H(2)O} (n) (NaCs-2) and {Na2.75Rb1.25[(PO3CH2CO2)(2)Mo5O15Cu(H2O)(3)]center dot 9H(2)O} (n) (NaRb-3), which were characterized by single-crystal X-ray diffraction, IR, TGA and elemental analysis. All three compounds are 1:1 polymers of the polyanion and the Cu2+ centers are all five-coordinate with two carboxylate oxygens in a trans fashion. However, the chains in KRb-1, NaCs-2 and NaRb-3 are packed differently along b leading to different solid state structures, indicating an important role of the alkali counter cations.
引用
收藏
页码:697 / 710
页数:14
相关论文
共 63 条
[1]  
Borras-Almenar J.J., 2004, POLYOXOMETALATE MOL
[2]   A building block approach to the synthesis of organic-inorganic oxide materials:: the hydrothermal synthesis and network structure of [{Ni4(tpypyz)3}{Mo5O15(O3PCH2CH2PO3)}2]•23H2O (tpypyz = tetra-2-pyridylpyrazine) [J].
Burkholder, E ;
Golub, V ;
O'Connor, CJ ;
Zubieta, J .
CHEMICAL COMMUNICATIONS, 2003, (17) :2128-2129
[3]   Solid-state coordination chemistry of the oxomolybdate-organodiphosphonate/nickel-organoimine system: Structural influences of the secondary metal coordination cation and diphosphonate tether lengths [J].
Burkholder, E ;
Golub, V ;
O'Connor, CJ ;
Zubieta, J .
INORGANIC CHEMISTRY, 2004, 43 (22) :7014-7029
[4]   Synthesis and structure of the two-dimensional bimetallic oxide [H4tphz]3[{Zn2(tphz)(H2O)4}{Mo5O15(O3PCH2CH2PO3)}4] • 14H2O:: the hydrothermal conversion of tetra-2-pyridylpyrazine to tetrapyrido [2,3-a:3′,2′-c:2",3"-h:3"′,2"′-j]phenazine (tphz) [J].
Burkholder, E ;
Zubieta, J .
INORGANICA CHIMICA ACTA, 2004, 357 (04) :1229-1235
[5]   Solid state coordination chemistry: One-, two-, and three-dimensional materials constructed from molybdophosphonate subunits linked through binuclear copper tetra-2-pyridylpyrazine groups [J].
Burkholder, E ;
Golub, V ;
O'Connor, CJ ;
Zubieta, J .
INORGANIC CHEMISTRY, 2003, 42 (21) :6729-6740
[6]   Solid state coordination chemistry:: construction of 2D networks and 3D frameworks from phosphomolybdate clusters and binuclear Cu(II) complexes.: The syntheses and structures of [{Cu2( tpypyz)(H2O)2}(Mo5O15)(HOPO3)2]•nH2O [n = 2, 3; tpypyz = tetra(2-pyridyl)pyrazine] [J].
Burkholder, E ;
Zubieta, J .
CHEMICAL COMMUNICATIONS, 2001, (20) :2056-2057
[7]   Polyoxometalates:: From inorganic chemistry to materials science [J].
Casañ-Pastor, N ;
Gómez-Romero, P .
FRONTIERS IN BIOSCIENCE-LANDMARK, 2004, 9 :1759-1770
[8]  
Champness NR, 2006, DALTON T, P877, DOI 10.1039/b512638j
[9]  
Cheetham AK, 1999, ANGEW CHEM INT EDIT, V38, P3268, DOI 10.1002/(SICI)1521-3773(19991115)38:22<3268::AID-ANIE3268>3.0.CO
[10]  
2-U