Prismane C_8: A New Form of Carbon?

Our numerical calculations on small carbon clusters point to the existence of a metastable three-dimensional eight-atom cluster C$_8$ which has a shape of a six-atom triangular prism with two excess atoms above and below its bases. We gave this cluster the name "prismane". The binding energy of the prismane equals to 5.1 eV/atom, i.e., is 0.45 eV/atom lower than the binding energy of the stable one-dimensional eight-atom cluster and 2.3 eV/atom lower than the binding energy of the bulk graphite or diamond. Molecular dynamics simulations give evidence for a rather high stability of the prismane, the activation energy for a prismane decay being about 0.8 eV. The prismane lifetime increases rapidly as the temperature decreases indicating a possibility of experimental observation of this cluster.Comment: 5 pages (revtex), 3 figures (eps

Systematic investigation of the influence of electronic substituents on dinuclear gold( i ) amidinates: synthesis, characterisation and photoluminescence studies

Dinuclear gold(I) compounds are of great interest due to their aurophilic interactions that influence their photophysical properties. Herein, we showcase that gold–gold interactions can be influenced by tuning the electronic properties of the ligands. Therefore, various para substituted (R) N,N′-bis(2,6-dimethylphenyl)formamidinate ligands (pRXylForm; Xyl = 2,6-dimethylphenyl and Form = formamidinate) were treated with Au(tht)Cl (tht = tetrahydrothiophene) to give via salt metathesis the corresponding gold(I) compounds [pRXylForm$_2$Au$_2$] (R = –OMe, –Me, –Ph, –H, –SMe, and –CO$_2$Me). All complexes showed intense luminescence properties at low temperatures. Alignment with the Hammett parameter σ$_p$ revealed the trends in the $^1$H and $^{13}$C NMR spectra. These results showed the influence of the donor–acceptor abilities of different substituents on the ligand system which were confirmed with calculated orbital energies. Photophysical investigations showed their lifetimes in the millisecond range indicating phosphorescence processes and revealed a redshift with the decreasing donor ability of the substituents in the solid state

Cooperativity in luminescent heterobimetallic diphosphine-β-diketiminate complexes

The bis(phosphine)-functionalized β-diketiminate ligand [HC{(CH$_3$)C}$_2${(o-[P(C$_6$H$_5$)$_2$]$_2$C$_6$H$_4$)N}$_2$]$^−$(PNac) was used for the synthesis of luminescent closed-shell bimetallic complexes. The PNNP pocket combining both soft and hard donor sites can act as an orthogonal ligand scaffold to selectively coordinate two different metal ions. Deprotonation and subsequent salt elimination with [AuCl(tht)] (tht = tetrahydrothiophene) or AgI yielded the mononuclear complexes [PNacAu] (1) or [PNacAg] (2), respectively. The AuI ion is linearly coordinated by the two phosphines, forming a 12-membered metalla-macrocycle with an empty β-diketiminate pocket available for complexation of hard d$^{10}$ metal ions (Zn$^{II}$, Cd$^{II}$, and Hg$^{II}$). According to this synthetic protocol, a series of heterobimetallic complexes were isolated. The complexation of the second metal ion in close spatial proximity has led to drastic changes in the photophysical properties. For further studies and understanding, quantum chemical calculations were performed

A cyclopentadienyl functionalized silylene-a flexible ligand for Si- And C-coordination

The synthesis of a 1,2,3,4-tetramethylcyclopentadienyl (Cp$^{4}$) substituted four-membered N-heterocyclic silylene [{PhC(NtBu) $_{2}$}Si(C$_{5}$Me$_{4}$H)] is reported first. Then, selected reactions with transition metal and a calcium precursor are shown. The proton of the Cp$_{4}$-unit is labile. This results in two different reaction pathways: (1) deprotonation and (2) rearrangement reactions. Deprotonation was achieved by the reaction of [{PhC(NtBu) $_{2}$}Si(C$_{5}$Me$_{4}$H)] with suitable zinc precursors. Rearrangement to [{PhC(NtBu) $_{2}$}(C$_{5}$Me$_{4}$)SiH], featuring a formally tetravalent silicon R$_{2}$CSi(R′)-H unit, was observed when the proton of the Cp$^{4}$ ring was shifted from the Cp$^{4}$-ring to the silylene in the presence of a Lewis acid. This allows for the coordination of the Cp$^{4}$-ring to a calcium compound. Furthermore, upon reaction with transition metal dimers [MCl(cod)] $_{2}$ (M = Rh, Ir; cod = 1,5-cyclooctadiene) the proton stays at the Cp$^{4}$-ring and the silylene reacts as a sigma donor, which breaks the dimeric structure of the precursors

A Phosphine‐ß‐diketiminate Nickel(I)‐Complex for Small Molecule Activation

A bis(diphenyl)-phosphine functionalized ß-diketimine ligand (PNac-H) was applied for the synthesis of a subvalent Ni(I) complex [PNac-Ni]. Here, the Ni(I) center is stabilized by a tetradentate PNNP-type pocket, forming a square planar coordination sphere. Subsequently, the Ni(I) complex was investigated with regard to its reactivity and the activation of small molecules. The reductive potential of Ni(I) enabled an activation of different substrate classes, such as CH$_2$X$_2$ (X=Br, I), I$_2$ or Ph$_2$E$_2$ (E=S, Se). The ligand\u27s design allows a stabilization of the reactive Ni(I) species while at the same time enabling activation processes due to a hemilabile coordination behavior and accessible axial coordination sites. The activation products have been characterized by single crystal X-ray diffraction, NMR and IR spectroscopy as well as elemental analysis

Dust in the Local Interstellar Wind

The gas-to-dust mass ratios found for interstellar dust within the Solar System, versus values determined astronomically for the cloud around the Solar System, suggest that large and small interstellar grains have separate histories, and that large interstellar grains preferentially detected by spacecraft are not formed exclusively by mass exchange with nearby interstellar gas. Observations by the Ulysses and Galileo satellites of the mass spectrum and flux rate of interstellar dust within the heliosphere are combined with information about the density, composition, and relative flow speed and direction of interstellar gas in the cloud surrounding the solar system to derive an in situ value for the gas-to-dust mass ratio, $R_{g/d} = 94^{+46}_{-38}$. Hubble observations of the cloud surrounding the solar system yield a gas-to-dust mass ratio of Rg/d=551+61-251 when B-star reference abundances are assumed. The exclusion of small dust grains from the heliosheath and heliosphere regions are modeled, increasing the discrepancy between interstellar and in situ observations. The shock destruction of interstellar grains is considered, and comparisons are made with interplanetary and presolar dust grains.Comment: 87 pages, 9 figures, 6 tables, accepted for publication in Astrophysical Journal. Uses AASTe

Magnetic Properties of Undoped C60C_{60}

The Heisenberg antiferromagnet, which arises from the large $U$ Hubbard model, is investigated on the $C_{60}$ molecule and other fullerenes. The connectivity of $C_{60}$ leads to an exotic classical ground state with nontrivial topology. We argue that there is no phase transition in the Hubbard model as a function of $U/t$, and thus the large $U$ solution is relevant for the physical case of intermediate coupling. The system undergoes a first order metamagnetic phase transition. We also consider the S=1/2 case using perturbation theory. Experimental tests are suggested.Comment: 12 pages, 3 figures (included

Fully Tin‐Coated Coinage Metal Ions: A Pincer‐Type Bis‐stannylene Ligand for Exclusive Tetrahedral Complexation

The synthesis of a novel bis-stannylene pincer ligand and its complexation with coinage metals (CuI, AgI and AuI) are described. All coinage metal centres are in tetrahedral coordination environments in the solid state and are exclusively coordinated by four neutral SnII donors. 119Sn NMR provided information about the behaviour in solution. All of the isolated compounds have photoluminescent properties, and these were investigated at low and elevated temperatures. Compared to the free bis-stannylene ligand, coordination to coinage metals led to an increase in the luminescence intensity. The new compounds were investigated in detail through all-electron relativistic density functional theory (DFT) calculations