University of Cambridge > > Electronic Structure Discussion Group > Trapping, linking and encapsulating molecules in metal-based complexes and cluster cages.

Trapping, linking and encapsulating molecules in metal-based complexes and cluster cages.

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Ab initio calculations are used to investigate three classes of systems composed of molecules inserted in complexes [1,2] and clusters [3]. One is based on trapping an organic molecule of appropriate structure between oppositely charged metal and non-metal ions. The systems are stabilized by a charge-transfer effectively through the molecule and can exhibit very large dipole moments. Further structural extensions are suggested in terms of such ion-trapping more than one molecule.

The other class employs a non-additivity of interactions between non-saturated organic molecules or even parts of the same molecule, separated by a metal atom. The system stability increases nonlinearly with the number of single metal-molecule “contacts” and is geometry-sensitive. Counterintuitive features are a weaker distortion and a larger separation of the system components bound more strongly.

Either type of the above two systems allows alignment and unusual connection of molecules, not occurring without the metal atoms. Possible extensions involve multiple junctions of both types combined into 1D to 3D metal-organic frameworks and nanostructures. Potential practical uses include energy storage in the metastable systems of the 1st type, design of strong metal-organic molecular interfaces in the systems of the 2nd type, new materials created from the units of both types, etc.

The last class is represented by molecules and molecular radicals inside metal-atom cages, for the cases of both non- and covalent interactions between them. The molecular core can alter the size of the shell via “inflating” it, and/or the shell shape adjusting to the symmetry of the “dopand”. Both variations may lead to related changes in the electronic properties of the systems. This could enable structure and property design of molecule-doped metal clusters, with likely applications in catalysis and new nanostructures.

[1] G. Kochhar and F.Y. Naumkin, New J. Chem. 34 (2010) 2932.
[2] F.Y. Naumkin, Chem. Phys. Lett. 499 (2010) 203.
[3] F.Y. Naumkin, in the RSC Monograph “Computational Nanoscience”, in press.

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