Molecular metals, structure

C.J. Ballhausen, Molecular Electronic Structures of Transition Metal Complexes, McGraw-Hill, New York, 1979. 

In 1992/1994, Grubbs et al. [29] and MacDiarmid et al. [30] described an improved precursor route to high molecular weight, structurally regular PPP 1, by transition metal-catalyzed polymerization, of the cyclohexa-1,3-diene derivative 14 to a stereoregular precursor polymer 16. The final step of the reaction sequence is the thermal, acid-catalyzed elimination of acetic acid, to convert 16 into PPP 1. They obtained unsupported PPP films of a definite structure, which were, however, badly contaminated with large amounts of polyphosphoric acid. 

Oxide- and Zeolite-supported "Molecular" Metal Clusters Synthesis, Structure, Bonding, and Catalytic Properties... 

Gates BC (2005) Oxide- and Zeolite-supported Molecular Metal Clusters Synthesis, Structure, Bonding, and Catalytic Properties. 16 211-231 Gibson SE (nee Thomas), Keen SP (1998) Cross-Metathesis. 1 155-181 Gisdakis P, see Rosch N (1999) 4 109-163 Gdrling A, see Rosch N (1999) 4 109-163... 

This approach of using 2D and 3D monodisperse nanoparticles in catalytic reaction studies ushers in a new era that will permit the identification of the molecular and structural features of selectivity [4,9]. Metal particle size, nanoparticle surface-structure, oxide-metal interface sites, selective site blocking, and hydrogen pressure have been implicated as important factors influencing reaction selectivity. We believe additional molecular ingredients of selectivity will be uncovered by coupling the synthesis of monodisperse nanoparticles with simultaneous studies of catalytic reaction selectivity as a function of the structural properties of these model nanoparticle catalyst systems. 

Fierro-Gonzalez, J.C., Kuba, S., Hao, Y. et al. (2006) Oxide- and zeolite-supported molecular metal complexes and clusters physical characterization and determination of structure, bonding, and metal oxidation state, J. Phys. Chem. B, 110, 13326. 

A major barrier to understanding fundamental relationships between molecular architecture, electronic structure, and charge transport in molecular metals derives from our inability to introduce poten-... 

These results illustrate that electrochemical techniques can be employed to synthesize a vast range of [Si(Pc)0]n-based molecular metals/conductive polymers with wide tunability in optical, magnetic, and electrical properties. Moreover, the structurally well-defined and well-ordered character of the polymer crystal structure offers the opportunity to explore structure/electro-chemical/collective properties and relationships to a depth not possible for most other conductive polymer systems. On a practical note, the present study helps to define those parameters crucial to the fabrication, from cheap, robust phthalocyanines, of efficient energy storage devices. 

Jaro, M. (2003), Metal threads in historical textiles, NATO Science Series, II Mathematics, Physics and Chemistry, Vol. 117 (Molecular and Structural Archaeology Cosmetic and Therapeutic Chemicals), pp. 163-178. 

A structural classification of 8 is difficult due to the fact that an arrangement of metal atoms as in 8 is uncommon in the whole field of molecular metal clusters. For this reason, detailed understanding of the bonding properties in 8 requires quantum chemical calculations. Theoretical analysis seems to be especially applicable to learning more about the bond between the two tetrahedra, which appears at first to be an isolated metal-metal bond between two metal atoms in the formal oxidation state zero. 

Fig. 1 Sketches of break junction-type test beds for molecular transport. On the far left is a tunneling electron microscopy (TEM) image of the actual metallic structure in (mechanical) break junctions from the nanoelectronics group at University of Basel. The sketches in the middle (Reprinted by permission from Macmillan Publishers Ltd Nature Nanotechnology 4, 230-234 (2009), copyright 2009) and right (reproduced from Molecular Devices, A.M. Moore, D.L. Allara, and P.S. Weiss, in NNIN Nanotechnology Open Textbook (2007) with permission from the authors) show possible geometries for molecules between two gold electrodes, and (on the upper right) a molecule that has only one end attached across the junction...

For a-Ga (coordination number 1 + 2 + 2 + 2) the short Ga-Ga bond distance of 2.45 A of every Ga atom with one of its seven neighbors is characteristic, so that a-Ga is also described as a molecular metal with Ga2 dumbbells. For the low-temperature phases / -, y-, and r)-Ca the following characteristic units are observed the ladder structure (coordination number 2 + 2 + 2 + 2) for /i-gallium, Gayrings that stack to form tubes and a centered Ga wire , observed for y-Ga, and interpenetrating Gan icosahedra for b-Ga. 

Some general comments on the solid-state chemistry ( From a molecular view on solids to molecules in solids ) have been reported by Simon (1995) emphasis was especially placed on the structural chemistry of metal-rich compounds formed by the metals in groups 1 to 6 and it was underlined that it is largely based on discrete and condensed clusters. In the chemistry of metals in low oxidation states, the residual valence electrons can be used for metal—metal bonding. Metal-rich compounds lie between normal valence compounds and the elemental metals themselves, with respect to their compositions, and often also with respect to their structures fragments of usual metal structures (close-packed, b.c.c., etc.) are often component units in the structures of metal-rich compounds. 

As far as SAM-controlled electrochemical metal deposition is concerned, substantial interest derives from microelectronics with its need to control the generation of interconnects and, thus, to understand the influence of organic layers on the metal nucleation and growth. However, the scope of this topic reaches well bqfond that, as illustrated by the substantial range of potential applications where small-scaled metal structures are of crucial importance, for example in electrochemical [31] and optical [32] sensing, molecular electronics [33], for plasmonics [34], or as metamaterials [35]. 

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