Modulating Paratropicity in Heteroarene-Fused Expanded Pentalenes.

Pentalenes are formally eight-π-electron antiaromatic, but π-expanded pentalenes can display varying levels of paratropicity depending on the choice of annelated (hetero)arenes and the geometry of π-expansion (i.e., linear vs bent topologies) around the [4n] core. Here, we explain the effects of annelation on the paratropicity of π-expanded pentalenes by relating the electronic structure of pentalenes to a pair of conjoined pentafulvenes.

Tunable Nano-Bending Structures of Loosened/Tightened Lassos with Bi-Stable Vibration-Induced Emissions for Multi-Manipulations of White-Light Emissions and Sensor Applications.

The first tunable nano-bending structures of [1]rotaxane containing a single-fluorophoric N,N'-diphenyl-dihydrodibenzo[a,c]phenazine (DPAC) moiety (i.e., [1]RA) are developed as a loosened lasso structure to feature the bright white-light emission [CIE (0.27, 0.33), Φ = 21.2%] in THF solution, where bi-stable states of bending and twisted structures of DPAC unit in [1]RA produce cyan and orange emissions at 480 and 600 nm, respectively. With acid/base controls, tunable loosened/tightened nano-loops of corresponding [1]rotaxanes (i.e., [1]RA/[1]RB) can be achieved via the shuttling of macrocycles reversibly, and thus to adjust their respective white-light/cyan emissions, where the cyan emission of [1]RB is obtained due to the largest conformational constraint of DPAC moiety in its bending form of [1]RB with a tightened lasso structure. Additionally, the non-interlocked analog M-Boc only shows the orange emission, revealing the twisted form of DPAC fluorophore in M-Boc without any conformational constraint. Moreover, the utilization of solvents (with different viscosities and polarities), temperatures, and water fractions could serve as effective tools to adjust the bi-stable vibration-induced emission (VIE) colors of [1]rotaxanes. Finally, tuning ratiometric emission colors of adaptive conformations of DPAC moieties by altering nano-bending structures in [1]rotaxanes and external stimuli can be further developed as intelligent temperature and viscosity sensor materials.

Tetra-tert-butyl-s-indacene is a Bond-Localized C2h Structure and a Challenge for Computational Chemistry.

Whether tetra-tert-butyl-s-indacene is a symmetric D2h structure or a bond-alternating C2h structure remains a standing puzzle. Close agreement between experimental and computed proton chemical shifts based on minima structures optimized at the M06-2X, ωB97X-D, and M11 levels confirm a bond-localized C2h symmetry, which is consistent with the expected strong antiaromaticity of TtB-s-indacene.

Cyclotetrabenzil Derivatives for Electrochemical Lithium-Ion Storage.

Organic electrode materials could revolutionize batteries because of their high energy densities, the use of Earth-abundant elements, and structural diversity which allows fine-tuning of electrochemical properties. However, small organic molecules and intermediates formed during their redox cycling in lithium-ion batteries (LIBs) have high solubility in organic electrolytes, leading to rapid decay of cycling performance. We report the use of three cyclotetrabenzil octaketone macrocycles as cathode materials for LIBs. The rigid and insoluble naphthalene-based cyclotetrabenzil reversibly accepts eight electrons in a two-step process with a specific capacity of 279 mAh g-1 and a stable cycling performance with ≈65 % capacity retention after 135 cycles. DFT calculations indicate that its reduction increases both ring strain and ring rigidity, as demonstrated by computed high distortion energies, repulsive regions in NCI plots, and close [C⋅⋅⋅C] contacts between the naphthalenes. This work highlights the importance of shape-persistency and ring strain in the design of redox-active macrocycles that maintain very low solubility in various redox states.

Fluxionality by quantum tunnelling: nonclassical 21-homododecahedryl cation rearrangement re-revisited.

The 21-homododecahedryl cation is a unique system in terms of its complete fluxionality based on two different rearrangements. In this work, we report the quantum tunneling effects that drive the reactions at temperatures where the semi-classical kinetics are impossible. We postulate that the tunnel effect in this system can serve to create a refrigerator that may operate at arbitrarily low temperatures.

Noble gas endohedral fullerenes.

This review focuses on the available experimental and theoretical investigations on noble gas (Ng) endohedral fullerenes, addressing essential questions related to the mutual effects that confinement of one or more Ng atoms induces on the electronic structure, bonding, and different properties of fullerenes. It also summarizes the different contributions to the mechanisms of formation and decomplexation, the reactivity towards Diels-Alder cycloaddition reactions, the chemical bonding situation of Ng endohedral fullerenes, and the interactions that dominate within these systems.

Fluxional Boron Clusters: From Theory to Reality.

Isolated boron clusters exhibit many intriguing properties, which have only recently been unfolding with the hand-in-hand advancement of state-of-the-art experimental and theoretical methods for the analyses of their electronic structure, chemical reactivity, and nuclear dynamics. A fascinating property that a number of these clusters display is fluxionality, a dynamical phenomenon associated with the delocalized nature of the chemical bonding and related to the continuous exchange between interatomic neighbors. The electron-deficient nature of boron is the driving force behind its extraordinary ability to form multicenter bonds, and this in turn leads to fluxional behavior only when an appropriate combination of topology and bonding is present. The first instance of fluxionality in boron clusters, the quasi-planar anion B19-, was reported in 2010. The rotational barrier of the inner B6 unit spinning within the peripheral B13 ring can be overcome even at low temperature, mimicking the characteristic motion of a rotary internal combustion engine, and hence, B19- was entitled a boron-based molecular Wankel engine. Shortly after that, it was found that other quasi-planar boron clusters, like B13+ and B182-, also exhibit an almost barrier-free rotation of internal planar moieties. The case of the B13+ cation is special because, on the one hand, it was chosen to examine the way to initiate, control, and direct the internal rotation using circularly polarized laser radiation, and on the other hand, the experimental manifestation of fluxionality was first established for this system through infrared experiments. Nevertheless, fluxional behavior is not limited to planar or pure boron clusters. Larger boron clusters, such as the fullerene-analogue borospherenes B40 and B39-, are also predicted to show pronounced dynamical behavior that is related to the interconversion between six- and seven-membered rings. Be6B11-, a triple-layer cluster, is another particularly interesting system since it exhibits multifold fluxionality consisting of the revolution of the outer boron ring around the Be6 core and the spinning of the two Be3 rings with respect to each other. The essential criteria for dynamical behavior in boron clusters are (1) the absence of a localized two-center, two-electron (2c-2e) bond between two molecular regions that tend to rotate with respect to each other, (2) the absence of steric hindrances for rotation and reorganization, and (3) retention of the delocalized electronic structure throughout the rotation/reorganization process. The fulfillment of the above three conditions ensures that low energy barriers will be associated with the rotation or reorganization of molecular moieties. The first two points can be illustrated from the facts that a single localized C-B σ bond in CB18 raises the rotational barrier by 27.0 kcal·mol-1 and the expansion of the outer ring by a single boron atom in moving from B12+ to B13+ lowers the rotational barrier by 7.5 kcal·mol-1. Alternatively, it is also possible to make a rigid boron cluster fluxional through doping, where the geometric and electronic changes caused by a suitable dopant, as in MB12- (M = Co, Rh, Ir) and B10Ca, reduce the corresponding rotational barriers enough to achieve fluxionality. At present, there are 13 pure boron clusters (B11-/0/+, B13+/0/-, B15+/0/-, B182-, B19-, and B20-/2-) and eight metal-doped boron clusters (B10Ca, NiB11-, [B2-Ta@B18]-, Be6B11-, Be6B102-, and MB18- (M = K, Rb, Cs)) that have sufficiently small rotational barriers (less than ∼1.5 kcal·mol-1) to exhibit fluxional behavior at low temperature. Some of the other reported boron clusters show more sizable barriers, and their dynamical behavior is manifested only at elevated temperatures. The research on such systems is driven by the notion that it ultimately will pave the way for the development of light-harvesting boron-based nanomotors/machines and robots, a reality that may not be that far away!

B10M2 (M = Rh, Ir): finally a stable boron-based icosahedral cluster.

The putative global minimum of clusters with formula B10M2 (M = Rh, Ir) corresponds to icosahedral structures formed by two alternately stacked B5 rings with the metals located at the top and bottom vertices. These structures are the closest approximation of molecular clusters to the elusive icosahedral boron. A detailed analysis of the chemical bonding revealed that the covalent character between the transition metal and the boron framework as well as the strong delocalization throughout the structure enhances the stabilization of the icosahedral form.

Li2B24: the simplest combination for a three-ring boron tube.

Herein we introduce a strategy employing lithium atoms as a scaffold to stabilize an embryo for boron tubes. The systematical exploration of the potential energy surface via evolutionary algorithms allowed us to find that Li2B24 adopts a tubular structure formed by three stacked rings of eight borons each with two lithium atoms capping the tube. The lithium atoms are essential for stabilization because of the strong electrostatic interaction between the Li cations and the boron framework, and concomitantly, they compensate for the energy cost of distorting a quasi-planar or double ring B24 cluster.

Structure and Bonding in CE5- (E=Al-Tl) Clusters: Planar Tetracoordinate Carbon versus Pentacoordinate Carbon.

The structure, bonding, and stability of clusters with the empirical formula CE5- (E=Al-Tl) have been analyzed by means of high-level computations. The results indicate that, whereas aluminum and gallium clusters have C2v structures with a planar tetracoordinate carbon (ptC), their heavier homologues prefer three-dimensional C4v forms with a pentacoordinate carbon center over the ptC one. The reason for such a preference is a delicate balance between the interaction energy of the fifth E atom with CE4 and the distortion energy. Moreover, bonding analysis shows that the ptC systems can be better described as CE4- , with 17-valence electrons interacting with E. The ptC core in these systems exhibits double aromatic (both σ and π) behavior, but the σ contribution is dominating.

Li2 B12 and Li3 B12 : Prediction of the Smallest Tubular and Cage-like Boron Structures.

An intriguing structural transition from the quasi-planar form of B12 cluster upon the interaction with lithium atoms is reported. High-level computations show that the lowest energy structures of LiB12 , Li2 B12 , and Li3 B12 have quasi-planar (Cs ), tubular (D6d ), and cage-like (Cs ) geometries, respectively. The energetic cost of distorting the B12 quasi-planar fragment is overcompensated by an enhanced electrostatic interaction between the Li cations and the tubular or cage-like B12 fragments, which is the main reason of such drastic structural changes, resulting in the smallest tubular (Li2 B12 ) and cage-like (Li3 B12 ) boron structures reported to date.

Coaxial Triple-Layered versus Helical Be6 B11- Clusters: Dual Structural Fluxionality and Multifold Aromaticity.

Two low-lying structures are unveiled for the Be6 B11- nanocluster system that are virtually isoenergetic. The first, triple-layered cluster has a peripheral B11 ring as central layer, being sandwiched by two Be3 rings in a coaxial fashion, albeit with no discernible interlayer Be-Be bonding. The B11 ring revolves like a flexible chain even at room temperature, gliding freely around the Be6 prism. At elevated temperatures (1000 K), the Be6 core itself also rotates; that is, two Be3 rings undergo relative rotation or twisting with respect to each other. Bonding analyses suggest four-fold (π and σ) aromaticity, offering a dilute and fluxional electron cloud that lubricates the dynamics. The second, helix-type cluster contains a B11 helical skeleton encompassing a distorted Be6 prism. It is chiral and is the first nanosystem with a boron helix. Molecular dynamics also shows that at high temperature the helix cluster readily converts into the triple-layered one.

Dynamical behavior of boron clusters.

Several of the lowest energy structures of small and medium sized boron clusters are two-dimensional systems made up of a pair of concentric rings. In some cases, the barriers to the rotation of one of those rings relative to the other are remarkably low. We find that a combination of electronic and geometrical factors, including apparently the relative sizes and symmetries of the inner and outer rings, are decisive for the diminished barriers to in-plane rotation in these two dimensional clusters. A sufficiently large outer ring is important; for instance, expansion of the outer ring by a single atom may reduce the barrier significantly. A crucial factor for an apparent rotation is that the σ-skeleton of the individual rings remains essentially intact during the rotation. Finally, the transition state for the rotation of the inner ring comprises the transformation of a square into a diamond, which may be linked to a mechanism suggested decades ago for the isomerization of carboranes and boranes.

The cubyl cation rearrangements.

Born-Oppenheimer molecular dynamics simulations and high-level ab initio computations predict that the cage-opening rearrangement of the cubyl cation to the 7H(+)-pentalenyl cation is feasible in the gas phase. The rate-determining step is the formation of the cuneyl cation with an activation barrier of 25.3 kcal mol(-1) at the CCSD(T)/def2-TZVP//MP2/def2-TZVP level. Thus, the cubyl cation is kinetically stable enough to be formed and trapped at moderate temperatures, but it may be rearranged at higher temperatures.

Nonclassical 21-Homododecahedryl Cation Rearrangement Revisited.

The degenerate rearrangement in the 21-homododecahedryl cation (1) has been studied via density functional theory computations and Born-Oppenheimer Molecular Dynamics simulations. Compound 1 can be described as a highly fluxional hyperconjugated carbocation. Complete scrambling of 1 can be achieved by the combination of two unveiled barrierless processes. The first one is a "rotation" of one of the six-membered rings via a 0.8 kcal·mol(-1) barrier, and the second one is a slower interconvertion between two hyperconjomers via an out-of-plane methine bending (ΔG(⧧) = 4.0 kcal·mol(-1)).

The 9-homocubyl cation rearrangement revisited.

Complexity of the potential energy surface of the 9-homocubyl cation is revealed by Born-Oppenheimer molecular dynamics simulations and high ab initio levels. The stereospecific automerizations observed experimentally involve bridged ions, which have either an aromatic or an anti-aromatic character. New pathways leading to more stable isomers are unveiled.

Structure and stability of (NG)nCN3Be3(+) clusters and comparison with (NG)BeY(0/+).

The noble gas binding ability of CN3Be3(+) clusters was assessed both by ab intio and density functional studies. The global minimum structure of the CN3Be3(+) cluster binds with four noble-gas (NG) atoms, in which the Be atoms are acting as active centers. The electron transfer from the noble gas to the Be atom plays a key role in binding. The dissociation energy of the Be-NG bond gradually increases from He to Rn, maintaining the periodic trend. The HOMO-LUMO gap, an indicator for stability, gives additional insight into these NG-bound clusters. The temperature at which the NG-binding process is thermodynamically feasible was identified. In addition, we investigated the stability of two new neutral NG compounds, (NG)BeSe and (NG)BeTe, and found them to be suitable candidates to be detected experimentally such as (NG)BeO and (NG)BeS. The dissociation energies of the Be-NG bond in monocationic analogues of (NG)BeY (Y=O, S, Se, Te) were found to be larger than in the corresponding neutral counter-parts. Finally, the higher the positive charge on the Be atoms, the higher the dissociation energy for the Be-NG bond becomes.