Molecular grid

Nitschke, J. R. Lehn, J.-M. Self-organized by selection generation of a metallosupra-molecular grid architecture by selection of components in a dynamic library of ligands. Proc. Natl. Acad. Sci. USA 2003, 100, 11970-11974. 

Interestingly, metal-metal interaction appears to be dependent on the oxidation state of the system. This is clearly evidenced by the results obtained for Os2 in liquid SO2 at —70°C, in that in these experimental conditions both the first and the second oxidation of each metal center can be seen (Fig. 5.4 Table 5.1).15 Potential splitting for the first oxidation process is 370 mV, whereas potential splitting for the second oxidation process is 150 mV. This result confirms the electron transfer pathway for the superexchange interaction once mono-oxidized, the Os(III)-based orbitals are stabilized and their interaction with the bridge-based LUMO orbitals decreases. A similar result has been recently obtained in molecular grids based on similar polypyridine ligands.25... 

Figure 10.39 X-ray molecular structures of (a) a [3X3] molecular grid, [Ag9(10.41)6]9+, (b) a [4X5] -Ag20 grid and (c) a decametallic quadruple helicate formed by 10.42 (Ag ions shown as large...

Molecular dynamics simulations on artificial surface-mounted molecular rotors have been performed and extensively reviewed.33 55 The theoretical rotational motion, driven by a circularly polarized electric field, of a dipolar chiral rhenium complex rotor attached to a molecular grid was also studied.56 In vacuum and at... 

The 3 x 3 square molecular grid [Ag9(Me2bpbpz)g]9+ (a) structural formula and (b) molecular structure. From [P. N. W. Baxter, J-M. Lehn,... 

Following directly from the initial part of the above study, Lehn et alP employed sequential complexation strategies to introduce different octahedral metal ions into 2x2 molecular grids of the type shown in Figure 7.17 each of these incorporates four molecules of 47. An important feature of the procedure was to introduce the respective metal ions sequentially in order of their increasing lability this was necessary to avoid scrambling of the metal centres. For this reason, ruthenium(II) or osmium(II) were introduced before iron(II), cobalt(II) or nickel(II). 

Figure 4.6.4 Molecular grid made of cellulose hairy rods...

Fig. 1 Synthesis of a 3 x 3 molecular grid. Physical studies indicate that recognition processes in this assembly involve solvation effects analogous to the hydrophobic effect. (Adapted from Ref. [16].)...

Table 3.1 compares experimental vertical ionization potentials [57] of CO2 and absolute values of orbital binding energies computed with the LBa potential. Molecular grids are constructed by a combination of spherical atomic grids covering large distances 20 A). The C-0 bond length is fixed at 1.162 A [58]. As one can see from... 

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