Networks anionic

Water exchange on cationic lanthanide chelates can also be influenced by the nature of the counter-anions (170,171). Anions like halides, sulfate, nitrate, acetate, and fluoroacetate impose different order on the second coordination shell around the chelate by influencing the hydrogen bond network. Anions with a high charge density like CU and S04 can break up the hydrogen bond network between water molecules around the metal center and by that, slow down the water exchange rate of the inner shell water molecule (171). 

In addition, alkali-ion transport is governed physically by the size of the bottlenecks (i.e. smallest opening at the site interface) between interstitial alkali-ion positions and chemically by the bonding energy between the mobile ions and the network anions. The shortest diameter of the bottlenecks should be larger than twice the sum of the mobile-ion and anion radii. The covalent bonding between the mobile ion and the anion network should be as weak as possible, which may be achieved if the anion forms a strong covalent complex with the network cations and/or if the anion is bonded to more than two of these cations. ... 

Phosphates are compoimds that contain oxyanions of phosphorus(V), ranging from the simple orthophosphate group to condensed chain, ring, and network anions. Oxyanions of phosphorus in lower oxidation states such as phosphite, HP03, are also known. 

Modifiers in glass are compounds that tend to donate anions to the network, whereas the cations occupy "holes" in the disordered stmcture. These conditions cause the formation of nonbridging anions, or anions that are connected to only one network-forming cation, as shown in Figure 2. Modifier compounds usually contain cations with low charge-to-radius ratios (Z/r), such as alkali or alkaline-earth ions. 

Thermoplastic Elastomers. These represent a whole class of synthetic elastomers, developed siace the 1960s, that ate permanently and reversibly thermoplastic, but behave as cross-linked networks at ambient temperature. One of the first was the triblock copolymer of the polystyrene—polybutadiene—polystyrene type (SheU s Kraton) prepared by anionic polymerization with organoHthium initiator. The stmcture and morphology is shown schematically in Figure 3. The incompatibiHty of the polystyrene and polybutadiene blocks leads to a dispersion of the spherical polystyrene domains (ca 20—30 nm) in the mbbery matrix of polybutadiene. Since each polybutadiene chain is anchored at both ends to a polystyrene domain, a network results. However, at elevated temperatures where the polystyrene softens, the elastomer can be molded like any thermoplastic, yet behaves much like a vulcanized mbber on cooling (see Elastomers, synthetic-thermoplastic elastomers). 

The diagrams also indicate why neutral c/oio-boranes BnHn4.2 are unknown since the 2 anionic charges are effectively located in the low-lying inwardly directed orbital which has no overlap with protons outside the cluster (e.g. above the edges or faces of the Bg oct edron). Replacement of the 6 Ht by 6 further builds up the basic three-dimensional network of hexaborides MB6 (p. 150) just as replacement of the 4 H in CH4 begins to build up the diamond lattice. 

The propensity for iodine to catenate is well illustrated by the numerous polyiodides which crystallize from solutions containing iodide ions and iodine. The symmetrical and unsymmetrical 13 ions (Table 17.15) have already been mentioned as have the I5- and anions and the extended networks of stoichiometry (Fig. 17.12). The stoichiometry of the crystals and the detailed geometry of the polyhalide depend sensitively on the relative concentrations of the components and the nature of the cation. For example, the linear ion may have the following dimensions ... 

An essential result of the simulations is that the Zintl anions Sn for the equimolar case do not survive in the liquid. They form (dynamical) networks. For the liquid with 80% of sodium, the suggested octet compounds SnNa4 do not exist, and only isolated tin atoms or tin dimers appear. 

More than 90% of the rocks and minerals found in the earth s crust are silicates, which are essentially ionic Typically the anion has a network covalent structure in which Si044-tetrahedra are bonded to one another in one, two, or three dimensions. The structure shown at the left of Figure 9.15 (p. 243), where the anion is a one-dimensional infinite chain, is typical of fibrous minerals such as diopside, CaSi03 - MgSi03. Asbestos has a related structure in which two chains are linked together to form a double strand. 

The organic resin material is often a styrene divinylbenzene (DVB) copolymer in a network or matrix, to which are attached functional groups such as a sulfonic acid, carboxylic acid, and quaternary ammonium. The nature of these groups determines whether the resin is classified as a strong/weak acid (cation resin) or strong/weak base (anion resin) ion-exchanger. 

Ammonium salts of the zeolites differ from most of the compounds containing this cation discussed above, in that the anion is a stable network of A104 and Si04 tetrahedra with acid groups situated within the regular channels and pore structure. The removal of ammonia (and water) from such structures has been of interest owing to the catalytic activity of the decomposition product. It is believed [1006] that the first step in deammination is proton transfer (as in the decomposition of many other ammonium salts) from NH4 to the (Al, Si)04 network with —OH production. This reaction is 90% complete by 673 K [1007] and water is lost by condensation of the —OH groups (773—1173 K). The rate of ammonia evolution and the nature of the residual product depend to some extent on reactant disposition [1006,1008]. 

Networks with labeled branch points have also been synthesized by anionic techniques. The crosslinks contain either ferrocene units 107) or lead, originating respectively from vinylferrocene or tetrakis[4(l-phenylvinyl)phenyl]plumbane 94). 

Networks obtained by anionic end-linking processes are not necessarily free of defects 106). There are always some dangling chains — which do not contribute to the elasticity of the network — and the formation of loops and of double connections cannot be excluded either. The probability of occurrence, of such defects decreases as the concentration of the reaction medium increases. Conversely, when the concentration is very high the network may contain entrapped entanglements which act as additional crosslinks. It remains that, upon reaction, the linear precursor chains (which are characterized independently) become elastically effective network chains, even though their number may be slightly lower than expected because of the defects. 

The purpose of this review is to show how anionic polymerization techniques have successfully contributed to the synthesis of a great variety of tailor-made polymer species Homopolymers of controlled molecular weight, co-functional polymers including macromonomers, cyclic macromolecules, star-shaped polymers and model networks, block copolymers and graft copolymers. 

The concept of silicates as inorganic polymers was implicit in the ideas developed by W. H. Zacheriasen in the early 1930s. He conceived of silicates as consisting of macromolecular structures held together by covalent bonds but including network-dwelling cations. These cations were not assumed to have a structural role but merely to be present in order to balance the charges on the anionic polymer network. 

Chiral-at-metal cations can themselves serve as chirality inducers. For example, optically pure Ru[(bipy)3] proved to be an excellent chiral auxihary for the stereoselective preparation of optically active 3D anionic networks [M(II)Cr(III)(oxalate)3]- n (with M = Mn, Ni), which display interesting magnetic properties. In these networks all of the metalhc centers have the same configuration, z or yl, as the template cation, as shown by CD spectroscopy and X-ray crystallography [43]. 

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