Gold clusters in

cluster chemistry In chemistry, an atom cluster (or simply cluster) is an ensemble of bound atoms or molecules that is intermediate in size between a simple molecule and a nanoparticle; that is, up to a few nanometers (nm) in diameter. The term ''microcluster' ...

are gold-derived materials that can either be discrete molecules or larger

colloid A colloid is a mixture in which one substance consisting of microscopically dispersed insoluble particles is suspended throughout another substance. Some definitions specify that the particles must be dispersed in a liquid, while others exten ...

al particles. Both types are described as

nanoparticle A nanoparticle or ultrafine particle is usually defined as a particle of matter that is between 1 and 100 nanometres (nm) in diameter. The term is sometimes used for larger particles, up to 500 nm, or fibers and tubes that are less than 10 ...

s, with diameters of less than one micrometer. A nanocluster is a collective group made up of a specific number of atoms or molecules held together by some interaction mechanism. Gold nanoclusters have potential applications in optoelectronics and catalysis.

Structure

Bulk gold exhibits a face-centered cubic (fcc) structure. As gold particle size decreases the fcc structure of gold transforms into a centered-icosahedral structure illustrated by . It can be shown that the fcc structure can be extended by a half unit cell in order to make it look like a cuboctahedral structure. The cuboctahedral structure maintains the cubic-closed pack and symmetry of fcc. This can be thought of as redefining the unit cell into a more complicated cell. Each edge of the cuboctahedron represents a peripheral Au–Au bond. The cuboctahedron has 24 edges while the icosahedron has 30 edges; the transition from cuboctahedron to icosahedron is favored since the increase in bonds contributes to the overall stability of the icosahedron structure. The centered icosahedral cluster is the basis of constructing large gold nanoclusters. is the endpoint of atom-by-atom growth. In other words, starting with one gold atom up to , each successful cluster is created by adding one additional atom. The icosahedral motif is found in many gold clusters through vertex sharing ( and ), face-fusion ( and ), and interpenetrating biicosahedrons (, , , and ). Large gold nanoclusters can essentially be reduced to a series of icosahedrons connecting, overlapping, and/or surrounding each other. The crystallization process of gold nanoclusters involves the formation of surface segments that grow towards the center of the cluster. The cluster assumes an icosahedral structure because of the associated surface energy reduction.

Discrete gold clusters

Well-defined, molecular clusters are known, invariably containing organic

ligand In coordination chemistry, a ligand is an ion or molecule ( functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's ele ...

s on their exteriors. Two examples are and . In order to generate naked gold clusters for catalytic applications, the ligands must be removed, which is typically done via a high-temperature ( or higher)

calcination Calcination refers to thermal treatment of a solid chemical compound (e.g. mixed carbonate ores) whereby the compound is raised to high temperature without melting under restricted supply of ambient oxygen (i.e. gaseous O2 fraction of air), gene ...

process, but can also be achieved chemically at low temperatures (below ), e.g. using a

peroxide In chemistry, peroxides are a group of compounds with the structure , where R = any element. The group in a peroxide is called the peroxide group or peroxo group. The nomenclature is somewhat variable. The most common peroxide is hydrogen ...

-assisted route.

Colloidal clusters

Gold clusters can be obtained in colloid form. Such colloids often occur with a surface coating of

alkanethiol In organic chemistry, a thiol (; ), or thiol derivative, is any organosulfur compound of the form , where R represents an alkyl or other organic substituent. The functional group itself is referred to as either a thiol group or a sulfhydryl grou ...

s or

protein Proteins are large biomolecules and macromolecules that comprise one or more long chains of amino acid residues. Proteins perform a vast array of functions within organisms, including catalysing metabolic reactions, DNA replication, respon ...

s. Such clusters can be used in

immunohistochemical staining Immunohistochemistry (IHC) is the most common application of immunostaining. It involves the process of selectively identifying antigens (proteins) in cells of a tissue section by exploiting the principle of antibodies binding specifically to a ...

. Gold metal nanoparticles (NPs) are characterized by an intense absorption in the visible region, which enhances the utility of these species for the development of completely optical devices. The wavelength of this

surface plasmon resonance Surface plasmon resonance (SPR) is the resonant oscillation of conduction electrons at the interface between negative and positive permittivity material in a particle stimulated by incident light. SPR is the basis of many standard tools for measu ...

(SPR) band depends on the size and shape of the nanoparticles as well as their interactions with the surrounding medium. The presence of this band enhances the utility of gold nanoparticle as building blocks for devices for data storage, ultrafast switching, and gas sensors. Whilst plasmonic gold nanoparticles only exhibit electric moments, clusters of such particles can exhibit magnetic moments making them of great interest for use in optical metamaterials

Gas-phase clusters

Evidence has been presented for the existence of hollow golden cages with the partial formula with ''n'' = 16 to 18. These clusters, with diameter of 550

picometre The picometre (international spelling as used by the International Bureau of Weights and Measures; SI symbol: pm) or picometer ( American spelling) is a unit of length in the International System of Units (SI), equal to , or one trillionth ...

s, are generated by laser vaporization and characterized by photoelectron spectroscopy. Using mass spectrometry, the unique tetrahedral structure of has been confirmed.

Catalysis

When implanted on a surface, gold clusters catalyze oxidation of at ambient temperatures. Similarly gold clusters implanted on can oxidize at temperatures as low as 40K. Catalytic activity correlated with the structure of gold nanoclusters. A strong relationship between energetic and electronic properties with size and structure of gold nanoclusters.

References

External links

* {{commons category inline, Gold clusters Cluster chemistry Gold compounds