Inorganic Chemistry Goes Protein Size: A Mo368 Nano-Hedgehog Initiating Nanochemistry by Symmetry Breaking

Abstract

Molybdenum monsters: A huge molybdenum cluster, comprising large areas with different local symmetry (in the picture different colors represent different (smaller) Mo fragments) is prepared and characterized. Molybdate fragments, which can tolerate a change of electron density at various positions, can be linked in a tremendous variety of ways according to a split‐and‐link process. Small changes of the boundary conditions, especially the redox conditions, which control growth, as well as the H+ ion concentration, can have a deciding influence on the process.

Large Semiconductor Molecules

“…This cluster is accessed using a combination of PhSSiMe 3 , S(SiMe 3 ) 2 and Figure 13.14, R ¼ Bu, Pr), arises from the straightforward reaction of PR 3 -solubilized AgO 2 CCF 3 with S(SiMe 3 ) 2 [64]. Cluster 19 represents the highest nuclearity semiconductor cluster that has been structurally characterized, and its size can be compared with that of the oxometallate of molybdenum, Na 48 [65]. The synthesis and structure of 19 contrast with all other silver-chalcogen nanoclusters in that these invariably require the use of chalcogenolate sources in order to ensure kinetic stabilization of the silverchalcogenide molecular core (see Sections 13.3.2 and 13.3.4).…”

Oxomolybdates: From Structures to Functions in a New Era of Nanochemistry

“…(Note that even the famous so-called bucky-ball {C 60 } fullerene molecule contains 12 pentagonal 'units'.) However, for the generation of more complex patterns, including negative as well as positive curvatures, that is showing symmetry breaking, a rather large number of negative and positive vertices with polygons of different kinds, for example including heptagons, is necessary [4]. [5] (see below).…”

“…The structure of the {Mo 368 } type cluster [4], the largest inorganic species known to date and also obtained from a special type of molybdenum blue solution, presents us with a paradigm shift with respect to symmetry breaking and changing curvatures in the nanocosmos. The phenomenon of symmetry breaking is visible at the surface due to the abundance of different large local symmetry areas as well as the presence of negative curvatures in between positive curvatures (see Figures 14.5 and 14.6).…”

Organometallic Nanoparticles of Metals or Metal Oxides

“…This size corresponds to proteins, to organic macromolecules like polymers or dendrimers or to small molecules which self-organize into micelles or vesicles. Inorganic molecular clusters [10] may also reach this size and display interesting physical properties [11]. Inorganic nanoparticles are in this respect of special interest, due to their many properties which may be exploited, up to practical applications.…”