Novel organotin-functionalized, polymeric transition metal cyanides: From Me3Sn- to Me2Sn(CH2) 3SnMe2 spacers

Schütze, Jens-Udo; Eckhardt, Rolf; Fischer, R.; Apperley, David C.; Davies, Norman; Harris, Robin K.

doi:10.1016/s0022-328x(96)06923-9

Cited by 19 publications

(5 citation statements)

References 11 publications

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“…The latter have flexible angular geometries at the O-donor, are complementary to hard lanthanide metal centers, and, therefore, form highly stable yet sterically flexible complex geometries. The only previously known examples of eightconnected frameworks have body-centered-cubic structures, [22][23][24] this structure representing the archetypal textbook lattice as found in CsCl. We report herein three unprecedented and unpredicted eight-connected networks that, for the first time, define non-CsCl topologies for eight-connected solid-state materials.…”

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confidence: 99%

Non‐Natural Eight‐Connected Solid‐State Materials: A New Coordination Chemistry

et al. 2004

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Molecular and materials science has provided a wide range of topologies and connectivities in the solid state. The most common nomenclature for such systems has been based [1][2][3] on the idea of two-, three-, four-, or six-connected materials in one, two and three dimensions. [4][5][6][7][8][9][10][11] Connectivities of five, seven, or higher are extremely rare, [12][13][14] and recent studies on inorganic/organic hybrid materials, especially in the area of metal-ligand coordination framework polymers, have enriched this area substantially. [15][16][17][18][19][20][21] However, highly connected materials remain scarce because the construction of such systems is severely hampered by the available number of coordination sites at the metal centers and the sterically demanding nature of organic ligands. Our design is based upon the combination of high coordination number lanthanide metal centers and 4,4'-bipyridine-N,N'-dioxide ligands. The latter have flexible angular geometries at the O-donor, are complementary to hard lanthanide metal centers, and, therefore, form highly stable yet sterically flexible complex geometries. The only previously known examples of eightconnected frameworks have body-centered-cubic structures, [22][23][24] this structure representing the archetypal textbook lattice as found in CsCl. We report herein three unprecedented and unpredicted eight-connected networks that, for the first time, define non-CsCl topologies for eight-connected solid-state materials.The compounds 1-3 have been obtained by slow diffusion of methanolic solutions of La(CF 3 SO 3 ) 3 , La(ClO 4 ) 3 , or Yb(CF 3 SO 3 ) 3 , respectively, and 4,4'-bipyridine-N,N'-dioxide (L) in MeOH in a U-tube through a buffering layer of CH 2 Cl 2 (for 1), CHCl 2 CHCl 2 (for 2), or C 2 Cl 4 (for 3). Compound 3 can also be prepared by covering the solid metal salt Yb(CF 3 SO 3 ) 3 with CH 2 Cl 2 or chlorobenzene and carefully layering with a solution of L in MeOH. Single-crystal X-ray structure determinations [25] of 1-3 confirm that they all have polymeric structures based on networks of eight-coordinated Ln III nodes linked by bridging L ligands. The asymmetric unit of 1 contains two independent La III centers. Although both are eight-coordinate, their coordination spheres are different. One La III center is bound by eight molecules of L, each bridging between the metal center and eight other La III centers. This, therefore, defines an eightconnected node within the structure. The second Ln III center is ligated with a molecule of MeOH and seven molecules of L with each of the latter bridging to seven other Ln III ions. This, therefore, defines a seven-connected node. At each metal center, four of the bridging ligands are used to generate a (4,4) net in which the remaining ligands are sited on the same side of the net linking to a second (4,4) net to give the observed bilayer motif. This affords three-and fourfold bridges from seven-and eight-connected centers, respectively, between the two (4,4) nets (Figure 1) with a tetragonal antipr...

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Non‐Natural Eight‐Connected Solid‐State Materials: A New Coordination Chemistry

et al. 2004

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“…2 Most effort has been directed to the controlled synthesis of architectures based on metal centres with 2-, 3-, 4-or 6-connectivity. However, metal-organic materials based upon 5-, 7-or 8-connected nodes are much rarer, [3][4][5][6][7] and are generally limited to metal centres with high co-ordination numbers and sterically non-demanding bridging ligands. We have previously prepared highly-connected nets using a combination of lanthanide (Ln) metal centres, which typically have co-ordination numbers ranging from 7 to 9, and 4,4A-bipyridine-N,NA-dioxide (L).…”

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Unprecedented bilayer topologies in 5- and 6-connected framework polymers

et al. 2004

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“…Connectivities of five, seven, or eight are extremely rare as a result of limitations in the symmetry or steric hindrance associated with connected nodes 7,8. Although the body‐centered cubic (bcu) net8a–c and the fluorite (flu) net8d are commonly seen in textbooks, such topologies with eight connecting nodes in a cubic geometry have only appeared in a few examples. To fulfill their geometric limitations, an eight‐coordinated metal center or an eight‐connecting polynuclear metal cluster block would be required; neither is easily achieved 8.…”

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confidence: 99%

Crystal Engineering: Toward Intersecting Channels from a Neutral Network with a bcu‐Type Topology

et al. 2005

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A great deal of interest has developed in the synthesis of metal-organic coordination polymers as they offer opportunities for preparing materials with controllable functionalities.[1] Although remarkable progress has been made in this new field of chemistry and materials science, largely due to efficient design strategies, [2,3] it is still difficult to prepare metal-organic frameworks with predictable topologies, even structures composed of simple inorganic salts.[4] The mimicking of topologies of natural minerals has rapidly become one of the most challenging issues in the design of metal-organic frameworks.[3c] Many 3D structures with mineral topologies such as NbO, quartz, pyrite, rutile, sodalite, CdSO 4 , and halite [5] have been reported recently from attempts to obtain geometric characteristics with designable functionalities. From the reported characterization of the net topologies, [6] all of these networks are based on the use of three-, four-, or six-connected building blocks.[5] Connectivities of five, seven, or eight are extremely rare as a result of limitations in the symmetry or steric hindrance associated with connected nodes. [7,8] Although the body-centered cubic (bcu) net [8a-c] and the fluorite (flu) net [8d] are commonly seen in textbooks, such topologies with eight connecting nodes in a cubic geometry have only appeared in a few examples. To fulfill their geometric limitations, an eight-coordinated metal center or an eight-connecting polynuclear metal cluster block would be required; neither is easily achieved.[8] The former has been obtained with eight-coordinated lanthanide ions or [M(CN) 8 ] 4À to form the bcu-type net, [8a,b] and the latter by using an eight-connecting cluster containing a tetracadmium carboxylate moiety and a four-connecting ligand to form the flu-type net. However, the bcu-type topology with only an eight-connecting polynuclear metal cluster unit has not yet been realized.As part of our ongoing efforts in the design and synthesis of functional crystalline materials, [3e] we report herein the rare, porous bcu-type framework of {[Cu 3 Cl 2 (4-ptz) 4 (H 2 O) 2 ]·3 DMF·5 H 2 O} n (1), assembled from 5-(4-pyridyl)-tetrazolate (4-ptz) as a bridging ligand and an eight-connecting tricopper cluster (Cu 3 Cl 2 4+ = Cu 3 cluster) as a building block. To the best of our knowledge, this is the first bcu-type structure with an eight-connecting polynuclear metal cluster unit, and represents one of the highest connected topologies known for coordination polymers. The appropriate choice of an organic ligand with specific functional groups and geometry is also a major factor in achieving this target. The reasons for using the 4-ptz ligand are twofold: first, the tetrazole group is a widely known alternative to a carboxylate moiety, and second, the five-membered heterocyclic tetrazole group, which contains four N donors and a pyridine group, could serve both as a potential active coordination site and a hydrogen-bond acceptor, thus permitting the polymeric framework to be ...

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Novel organotin-functionalized, polymeric transition metal cyanides: From Me3Sn- to Me2Sn(CH2) 3SnMe2 spacers

Cited by 19 publications

References 11 publications

Non‐Natural Eight‐Connected Solid‐State Materials: A New Coordination Chemistry

Non‐Natural Eight‐Connected Solid‐State Materials: A New Coordination Chemistry

Unprecedented bilayer topologies in 5- and 6-connected framework polymers

Crystal Engineering: Toward Intersecting Channels from a Neutral Network with a bcu‐Type Topology

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