Structural interconnections and the role of heptagonal rings in endohedral trimetallic nitride template fullerenes.

Recent experiments indicate that fullerene isomers outside the classical definition can also encapsulate metallic atoms or clusters to form endohedral metallofullerenes. Our systematic study using DFT calculations, suggests that many heptagon-including nonclassical trimetallic nitride template fullerenes are similar in stability to their classical counterparts, and that conversion between low-energy nonclassical and classical parent cages via Endo-Kroto insertion/extrusion of C2 units and Stone-Wales isomerization may facilitate the formation of endohedral trimetallic nitride fullerenes. Close structural connections are found between favored isomers of trimetallic nitride template fullerenes from C78 to C82 . It appears that the lower symmetry and local deformations associated with introduction of a heptagonal ring favor encapsulation of intrinsically less symmetrical mixed metal nitride clusters

When is a symmetric pin-jointed framework isostatic?

Maxwell's rule from 1864 gives a necessary condition for a framework to be isostatic in 2D or in 3D. Given a framework with point group symmetry, group representation theory is exploited to provide further necessary conditions. This paper shows how, for an isostatic framework, these conditions imply very simply stated restrictions on the numbers of those structural components that are unshifted by the symmetry operations of the framework. In particular, it turns out that an isostatic framework in 2D can belong to one of only six point groups. Some conjectures and initial results are presented that would give sufficient conditions (in both 2D and 3D) for a framework that is realized generically for a given symmetry group to be an isostatic framework.Comment: 24 pages, 10 figures; added references, minor changes, revised last paragrap

Spectra and structural polynomials of graphs of relevance to the theory of molecular conduction

In chemistry and physics, distortivity of π-systems (stabilisation of bond-alternated structures) is an important factor in the calculation of geometric, energetic, and electronic properties of molecules via graph theoretical methods. We use the spectra of paths and cycles with alternating vertex and edge weights to obtain the eigenvalues and eigenvectors for a class of linear and cyclic ladders with alternating rung and backbone edge weights. We derive characteristic polynomials and other structural polynomials formed from the cofactors of the characteristic matrix for these graphs. We also obtain spectra and structural polynomials for ladders with flipped weights and/or Möbius topology. In all cases, the structural polynomials for the composite graphs are expressed in terms of products of polynomials for graphs of half order. This form of the expressions allows global deductions about the transmission spectra of molecular devices in the graph-theoretical theory of ballistic molecular conduction

Perimeter ring currents in benzenoids from Pauling bond orders

It is shown that the ring currents in perimeter hexagonal rings of Kekulean benzenoids, as estimated within the Randić conjugated-circuit model, can be calculated directly without tedious pairwise comparison of Kekulé structures or Kekulé counting for cycle-deleted subgraphs. Required are only the Pauling bond orders of perimeter bonds and the number of Kekulé structures of the benzenoid, both readily available from the adjacency matrix of the carbon skeleton. This approach provides easy calculation of complete current maps for benzenoids in which every face has at least one bond on the perimeter (as in the example of cata-condensed benzenoids), and allows qualitative evaluation of the main ring-current contributions to 1H chemical shifts in general benzenoids. A combined Randić- Pauling model for correlation of ring current and bond length through bond order is derived and shown to be consistent with resilience of current under bond alternation

Effect of Ring Size and Migratory Groups on [1,n] Suprafacial Shift Reactions. Confirmation of Aromatic and Antiaromatic Transition-State Character by Ring-Current Analysis

Suprafacial sigmatropic shift reactions of 5-substituted cyclopentadienes, 3-substituted cyclopropenes, and 7-substituted cycloheptatrienes have been studied computationally at the MP2/6-31+G* level for structures and energetics, and using the ipsocentric method at the CHF/6-31G** level to calculate current-density maps. The hydrogen shifts in cyclopentadienes have a diatropic ring currents indicating aromatic, cyclopentadienide anion character. This result stands in contrast to the fluorine shift in 5- fluorocyclopentadiene which requires much more energy, and has a paratropic ring current in the TS pointing to antiaromatic, cyclopentadienyl cation character. [1,3] hydrogen shifts in cyclopropenes are very difficult, passing through transition states that have an extended C-C bond. For 3-fluorocyclopropene the [1,3] fluorine shift is much easier than the hydrogen shift. For 7-fluorocycloheptatriene the [1,7] hydrogen shift is predicted, but requires very high energy and has a paratropic ring current and antiaromatic character. The [1,7] suprafacial fluorine shift is relatively easy, having a TS with cycloheptatrienyl cation character. Patterns of currents, and the reversal for H and F migration, are rationalized by orbital analysis based on the ipsocentric method. Calculated charges and structural features for reactants and transition states support these conclusions

An atlas of endohedral Sc2S cluster fullerenes

Structural identification is a difficult task in the study of metallofullerenes, but understanding of the mechanism of formation of these structures is a pre-requisite for new high-yield synthetic methods. Here, systematic density functional theory calculations demonstrate that metal sulfide fullerenes Sc2S@Cn have similar cage geometries from C70 to C84 and form a close-knit family of structures related by Endo-Kroto insertion/extrusion of C2 units and Stone-Wales isomerization transformations. The stabilities predicted for favoured isomers by DFT calculations are in good agreement with available experimental observations, have implications for the formation of metallofullerenes, and will aid structural identification from within the combinatorially vast pool of conceivable isomers

A simple model of ballistic conduction in multi-lead molecular devices

A fully analytical model is presented for ballistic conduction in a multi-lead device that is based on a π-conjugated carbon framework attached to a single source lead and several sink leads. This source-and-multiple-sink potential (SMSP) model is rooted in the Ernzerhof source-and-sink potential (SSP) approach and specifies transmission in terms of combinations of structural polynomials based on the molecular graph. The simplicity of the model allows insight into many-lead devices in terms of constituent two-lead devices, description of conduction in the multi-lead device in terms of structural polynomials, molecular orbital channels, and selection rules for active and inert leads and orbitals. In the wide-band limit, transmission can be expressed entirely in terms of characteristic polynomials of vertex-deleted graphs. As limiting cases of maximum connection, complete symmetric devices (CSD) and complete bipartite symmetric devices (CBSD) are defined and solved analytically. These devices have vanishing lead-lead interference effects. Illustrative calculations of transmission curves for model small-molecule systems are presented and selection rules are identified

Near omni-conductors and insulators: Alternant hydrocarbons in the SSP model of ballistic conduction

Within the source-and-sink-potential model, a complete characterisation is obtained for the conduction behaviour of alternant π-conjugated hydrocarbons (conjugated hydrocarbons without odd cycles). In this model, an omni-conductor has a molecular graph that conducts at the Fermi level irrespective of the choice of connection vertices. Likewise, an omni-insulator is a molecular graph that fails to conduct for any choice of connections. We give a comprehensive classification of possible combinations of omni-conducting and omni-insulating behaviour for molecular graphs, ranked by nullity (number of non-bonding orbitals). Alternant hydrocarbons are those that have bipartite molecular graphs; they cannot be full omni-conductors or full omni-insulators but may conduct or insulate within well-defined subsets of vertices (unsaturated carbon centres). This leads to the definition of "near omni-conductors" and "near omni-insulators." Of 81 conceivable classes of conduction behaviour for alternants, only 14 are realisable. Of these, nine are realised by more than one chemical graph. For example, conduction of all Kekulean benzenoids (nanographenes) is described by just two classes. In particular, the catafused benzenoids (benzenoids in which no carbon atom belongs to three hexagons) conduct when connected to leads via one starred and one unstarred atom, and otherwise insulate, corresponding to conduction type CII in the near-omni classification scheme

A curious family of convex benzenoids and their altans

The altan graph of G, a(G, H), is constructed from graph G by choosing an attachment set H from the vertices of G and attaching vertices of H to alternate vertices of a new perimeter cycle of length 2|H|. When G is a polycyclic plane graph with maximum degree 3, the natural choice for the attachment set is to take all perimeter degree-2 vertices in the order encountered in a walk around the perimeter. The construction has implications for the electronic structure and chemistry of carbon nanostructures with molecular graph a(G, H), as kernel eigenvectors of the altan correspond to non-bonding π molecular orbitals of the corresponding unsaturated hydrocarbon. Benzenoids form an important subclass of carbon nanostructures. A convex benzenoid has a boundary on which all vertices of degree 3 have exactly two neighbours of degree 2. The nullity of a graph is the dimension of the kernel of its adjacency matrix. The possible values for the excess nullity of a(G, H) over that of G are 2, 1, or 0. Moreover, altans of benzenoids have nullity at least 1. Examples of benzenoids where the excess nullity is 2 were found recently. It has been conjectured that the excess nullity when G is a convex benzenoid is at most 1. Here, we exhibit an infinite family of convex benzenoids with 3-fold dihedral symmetry (point group D3h) where nullity increases from 2 to 3 under altanisation. This family accounts for all known examples with the excess nullity of 1 where the parent graph is a singular convex benzenoid

Distributed curvature and stability of fullerenes

Energies of non-planar conjugated π systems are typically described qualitatively in terms of the balance of π stabilisation and the steric strain associated with geometric curvature. Curvature also has a purely graph-theoretical description: combinatorial curvature at a vertex of a polyhedral graph is defined as one minus half the vertex degree plus the sum of reciprocal sizes of the faces meeting at that vertex. Prisms and antiprisms have positive combinatorial vertex curvature at every vertex. Excluding these two infinite families, we call any other polyhedron with everywhere positive combinatorial curvature a PCC polyhedron. Cubic PCC polyhedra are initially common, but must eventually die out with increasing vertex count; the largest example constructed so far has 132 vertices. The fullerenes Cn have cubic polyhedral molecular graphs with n vertices, 12 pentagonal and (n/2 − 10) hexagonal faces. We show that there are exactly 39 PCC fullerenes, all in the range 20 ≤ n ≤ 60. In this range, there is only partial correlation between PCC status and stability as defined by minimum pentagon adjacency. The sum of vertex curvatures is 2 for any polyhedron; for fullerenes the sum of squared vertex curvatures is linearly related to the number of pentagon adjacencies and hence is a direct measure of relative stability of the lower (n ≤ 60) fullerenes. For n ≥ 62, non-PCC fullerenes with a minimum number of pentagon adjacencies minimise mean-square curvature. For n ≥ 70, minimum mean-square curvature implies isolation of pentagons, which is the strongest indicator of stability for a bare fullerene