From Designer Clusters to Synthetic Crystalline Nanoassemblies

Castleman, A. W.; Khanna, Shiv N.; Sen, Ayusman; Reber, Arthur C.; Qian, Meichun; Davis, Kevin; Peppernick, Samuel J.; Ugrinov, Angel; Merritt, Mark D.

doi:10.1021/nl071224j

Cited by 110 publications

(104 citation statements)

References 26 publications

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“…[1][2][3] However, the difficulty in obtaining crystalline materials which are needed for X-ray crystal analysis has hindered the determination of the atomic structure in nanomaterials. This difficulty is known as the "nanostructure problem" and hinders the study of structure-property relationships in these materials.…”

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confidence: 99%

The effect of cluster size on the optical band gap energy of Zn-based metal–organic frameworks

et al. 2015

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We have synthesized three Metal-Organic Frameworks (MOFs) in which Zn metal ions form the secondary building unit, and 4,4'-sulfonyldibenzoic acid (SDB) serves as the ligand: [[Zn(DMF)(SDB)](DMF), 1, [Zn(3)(DMF)(3)(SDB)(3)](DMF), 2 and [Zn(3)(OH)(2)(SDB)(2)] (DMF)(2), 3, where DMF = dimethyl formamide]. Compound contains a paddle-wheel type Zn dimer, compound contains a Zn trimer motif, and contains a one-dimensional Zn-OH-Zn chain. These building units may be considered to be Zn clusters. We have measured and theoretically calculated the band gap energy and by theoretical investigations we found that the cluster size plays an important role in the band gap energy, however additional effects are observed. The larger cluster size corresponds to a larger band gap energy, however the cavity of the trimer based compound (2) traps a solvent molecule that decreases the band gap energy.

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The effect of cluster size on the optical band gap energy of Zn-based metal–organic frameworks

et al. 2015

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“…The corresponding energy eigenvalues can be grouped into atomic-like shells (1S, 1P, 1D, 2S, 1F, 2P, …), depending on the degeneracy and spatial symmetry of the molecular orbitals. Unlike the atoms, the physical and chemical properties of superclusters can be tailored through selection of size and composition, making them very promising building blocks for new materials2526.…”

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Design of Three-shell Icosahedral Matryoshka Clusters A@B12@A20 (A = Sn, Pb; B = Mg, Zn, Cd, Mn)

Huang

Zhao

et al. 2014

Sci Rep

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We propose a series of icosahedral matryoshka clusters of A@B12@A20 (A = Sn, Pb; B = Mg, Zn, Cd), which possess large HOMO-LUMO gaps (1.29 to 1.54 eV) and low formation energies (0.06 to 0.21 eV/atom). A global minimum search using a genetic algorithm and density functional theory calculations confirms that such onion-like three-shell structures are the ground states for these A21B12 binary clusters. All of these icosahedral matryoshka clusters, including two previously found ones, i.e., [As@Ni12@As20]3− and [Sn@Cu12@Sn20]12−, follow the 108-electron rule, which originates from the high Ih symmetry and consequently the splitting of superatom orbitals of high angular momentum. More interestingly, two magnetic matryoshka clusters, i.e., Sn@Mn12@Sn20 and Pb@Mn12@Pb20, are designed, which combine a large magnetic moment of 28 µB, a moderate HOMO-LUMO gap, and weak inter-cluster interaction energy, making them ideal building blocks in novel magnetic materials and devices.

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“…Further Al 13 has a large electron affinity of 3.4 eV close to that of a Cl atom (9). These analogies have prompted the concept that selected stable clusters could mimic the electronic behavior of elemental atoms and be classified as superatoms forming a third dimension of the periodic table (10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21). Because the properties of clusters change with size and composition, the superatoms offer the prospect of serving as the building blocks of nanomaterials with tunable characteristics (16,18).…”

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Hund’s rule in superatoms with transition metal impurities

Medel

Reveles

Khanna

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

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The quantum states in metal clusters bunch into supershells with associated orbitals having shapes resembling those in atoms, giving rise to the concept that selected clusters could mimic the characteristics of atoms and be classified as superatoms. Unlike atoms, the superatom orbitals span over multiple atoms and the filling of orbitals does not usually exhibit Hund's rule seen in atoms. Here, we demonstrate the possibility of enhancing exchange splitting in superatom shells via a composite cluster of a central transition metal and surrounding nearly free electron metal atoms. The transition metal d states hybridize with superatom D states and result in enhanced splitting between the majority and minority sets where the moment and the splitting can be controlled by the nature of the central atom. We demonstrate these findings through studies on TMMg n clusters where TM is a 3d atom. The clusters exhibit Hund's filling, opening the pathway to superatoms with magnetic shells.magnetic superatoms | jellium model | superatomic shells T he quantum confinement of electrons in small compact symmetric metal clusters results in electronic shell sequence 1S, 1P, 1D, …, much in the same way as in atoms. This analogy, originally introduced through the electronic states in a "jellium sphere" where the electron gas is confined to a uniform positive background of the size of the cluster, extends beyond this oversimplified model (1-9). Numerous first principles electronic structure studies on metal clusters have demonstrated the close grouping of electronic states into shells and have further shown that the shapes of the cluster electronic orbitals resemble those in atoms. Experiments on the reactivity of clusters have provided evidence that clusters and atoms of similar valence shells exhibit analogous chemical patterns. For example, although bulk aluminum is readily oxidized by oxygen, an Al 13 − cluster with filled 1S 2 , 1P 6 , 1D 10 , 2S 2 , 1F 14 , and 2P 6 shells exhibits strong resistance to etching by oxygen typical of inert atoms (5, 10). Further Al 13 has a large electron affinity of 3.4 eV close to that of a Cl atom (9). These analogies have prompted the concept that selected stable clusters could mimic the electronic behavior of elemental atoms and be classified as superatoms forming a third dimension of the periodic table (10-21). Because the properties of clusters change with size and composition, the superatoms offer the prospect of serving as the building blocks of nanomaterials with tunable characteristics (16,18).The electronic orbitals in superatoms, although resembling those in real atoms in shape, do spread over multiple atoms. This affects the way in which the electrons fill the shells because of two competing effects. Hund's rule favors high spin states in open shell systems stabilized by exchange coupling, and indeed higher spin multiplicities have been seen in some clusters (22) and even quantum dots spanning several nanometers (23). However, unlike the case of atoms, small clusters can undergo structu...

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From Designer Clusters to Synthetic Crystalline Nanoassemblies

Cited by 110 publications

References 26 publications

The effect of cluster size on the optical band gap energy of Zn-based metal–organic frameworks

The effect of cluster size on the optical band gap energy of Zn-based metal–organic frameworks

Design of Three-shell Icosahedral Matryoshka Clusters A@B12@A20 (A = Sn, Pb; B = Mg, Zn, Cd, Mn)

Hund’s rule in superatoms with transition metal impurities

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