Presenting an accurate yet efficient plane-wave DFT approach for the computational exploration of the bulk properties of the super-heavy main-group elements including copernicium (Cn–Og, Z = 112–118).

A relation M_{SHS→LJ} between the set of nonisomorphic sticky-hard-sphere clusters M_{SHS} and the sets of local energy minima M_{LJ} of the (m,n)-Lennard-Jones potential V_{mn}^{LJ}(r)=ɛ/n-m[mr^{-n}-nr^{-m}] is established. The number of nonisomorphic stable clusters depends strongly and nontrivially on both m and n and increases exponentially with increasing cluster size N for N≳10. While the map from M_{SHS}→M_{SHS→LJ} is noninjective and nonsurjective, the number of Lennard-Jones structures missing from the map is relatively small for cluster sizes up to N=13, and most of the missing structures correspond to energetically unfavorable minima even for fairly low (m,n). Furthermore, even the softest Lennard-Jones potential predicts that the coordination of 13 spheres around a central sphere is problematic (the Gregory-Newton problem). A more realistic extended Lennard-Jones potential chosen from coupled-cluster calculations for a rare gas dimer leads to a substantial increase in the number of nonisomorphic clusters, even though the potential curve is very similar to a (6,12)-Lennard-Jones potential.

Golden fullerenes have recently been identified by photoelectron spectra by Bulusu et al. [S. Bulusu, X. Li, L.-S. Wang, X. C. Zeng, PNAS 2006, 103, 8326-8330]. These unique triangulations of a sphere are related to fullerene duals having exactly 12 vertices of degree five, and the icosahedral hollow gold cages previously postulated are related to the Goldberg-Coxeter transforms of C20 starting from a triangulated surface (hexagonal lattice, dual of a graphene sheet). This also relates topologically the (chiral) gold nanowires observed to the (chiral) carbon nanotubes. In fact, the Mackay icosahedra well known in gold cluster chemistry are related topologically to the dual halma transforms of the smallest possible fullerene C20 . The basic building block here is the (111) fcc sheet of bulk gold which is dual to graphene. Because of this interesting one-to-one relationship through Euler's polyhedral formula, there are as many golden fullerene isomers as there are fullerene isomers, with the number of isomers Niso increasing polynomially as O(Niso9 ). For the recently observed Au16- , Au17- , and Au18- we present simulated photoelectron spectra including all isomers. We also predict the photoelectron spectrum of Au32- . The stability of the golden fullerenes is discussed in relation with the more compact structures for the neutral and negatively charged Au12 to Au20 and Au32 clusters. As for the compact gold clusters we observe a clear trend in stability of the hollow gold cages towards the (111) fcc sheet. The high stability of the (111) fcc sheet of gold compared to the bulk 3D structure explains the unusual stability of these hollow gold cages.

The novel all-hydrocarbon ligand-stabilized binuclear clusters of metal-core composition Ni2Zn7E, [(η(5)-Cp*)Ni2(ZnMe)6(ZnCp*)(ECp*)] (1-Zn, E = Zn; 1-Ga, E = Ga) and [(η(6)-toluene)Ni2(ZnCp*)2(ZnMe)6] (2; Cp* = pentamethylcyclopentadienyl), were obtained via Ga/Zn and Al/Zn exchange reactions using the starting compounds [Ni2(ECp*)3(η(2)-C2H4)2] (E = Al/Ga) and an excess of ZnMe2 (Me = CH3). Compounds 1-Zn and 1-Ga are very closely related and differ only by one Zn or Ga atom in the group 12/13 metal shell (Zn/Ga) around the two Ni centers. Accordingly, 1-Zn is EPR-active and 1-Ga is EPR-silent. The compounds were derived as a crystalline product mixture. All new compounds were characterized by (1)H and (13)C NMR and electron paramagnetic resonance (EPR) spectroscopy, mass spectrometric analysis using liquid-injection field desorption ionization, and elemental analysis, and their molecular structures were determined by single-crystal X-ray diffraction studies. In addition, the electronic structure has been investigated by DFT and QTAIM calculations, which suggest that there is a Ni1-Ni2 binding interaction. Similar to Zn-rich intermetallic phases of the Hume-Rothery type, the transition metals (here Ni) are distributed in a matrix of Zn atoms to yield highly Zn-coordinated environments. The organic residues, ancillary ligands (Me, Cp*, and toluene), can be viewed as the "protecting" shell of the 10-metal-atom core structures. The soft and flexible binding properties of Cp* and transferability of Me substituents between groups 12 and 13 are essential for the success of this precedence-less type of cluster formation reaction.

Herein, we present a series of isomerically pure, peripherally alkyl substituted, soluble and low aggregating azaphthalocyanines as well as their new, smaller hybrid homologues, azasubphthalocyanines. The focus lies on the effect of the systematically increasing number of aza building blocks [-N[double bond, length as m-dash]] replacing the non-peripheral [-CH[double bond, length as m-dash]] units and their influence on the physical and photophysical properties of these chromophores. The absolute and relative HOMO-LUMO energies of azaphthalocyanines were analyzed using UV-Vis and CV and compared to the density functional theory calculations (B3LYP, TD-DFT). The lowering of the HOMO level is revealed as the determining factor for the trend in the adsorption energies by electronic structure analysis. Crystals of substituted subphthalocyanines, N2-Pc*H2 and N4-[Pc*Zn·H2O], were obtained out of DCM. For the synthesis of the valuable tetramethyltetralin phthalocyanine building block a new highly efficient synthesis involving a nearly quantitative CoII catalyzed aerobic autoxidation step is introduced replacing inefficient KMnO4/pyridine as the oxidant.