Halogen bonding between an isoindoline nitroxide and 1,4-diiodotetrafluorobenzene: new tools and tectons for self-assembling organic spin systems

Halogen bonding has been observed for the first time between an isoindoline nitroxide and an iodoperfluorocarbon (see figure), which cocrystallize to form a discrete 2:1 supramolecular compound in which NO.⋅⋅⋅I halogen bonding is the dominant intermolecular interaction. This illustrates the potential use of halogen bonding and isoindoline nitroxide tectons for the assembly of organic spin systems...

Spin-coated carbon

We describe a novel and facile approach to covalently graft molecules containing stable free radicals onto carbon surfaces including graphene, carbon nanotubes, glassy carbon and carbon fibres. The new technique employs a stable aryl nitroxide radical diazonium tetrafluoroborate salt. The salt may be isolated and added to carbon surfaces in solution, suspension or electrochemically and represents a convenient, versatile and highly efficient means to adorn graphitic materials with large numbers of free radical spin systems

Vapour phase assembly of a halogen bonded complex of an isoindoline nitroxide and 1,2-diiodotetrafluorobenzene

Vapour phase assembly has been used for the first time to prepare co-crystals in which the primary intermolecular interaction is halogen bonding. Co-crystals of the nitroxide 1,1,3,3-tetramethylisoindolin-2-yloxyl (TMIO) and 1,2-diiodotetrafluorobenzene (1,2-DITFB) are readily formed under standard sublimation conditions. Single crystal X-ray diffraction confirmed the structure of a 2:2 cyclic tetramer, (TMIO)2·(1,2-DITFB)2, which exhibits a new halogen bonding motif, with each nitroxide oxygen atom accepting two halogen bonds. Powder X-ray diffraction confirmed the homogeneity of the bulk sample. The crystalline complex was further characterized in the solid state using thermal analysis and vibrational spectroscopy (infrared and Raman). Density functional theory calculations were also used to evaluate the enthalpy of formation, electrostatic potential and unpaired electron density of the complex. These findings illustrate the preparation of co-crystals where solution state methodology is problematic and the potential of this approach for the formation of novel organic spin systems.

One-step macroscopic alignment of conjugated polymer systems by epitaxial crystallization during spin-coating

The one-step preparation of highly anisotropic polymer semiconductor thin films directly from solution is demonstrated. The conjugated polymer poly(3-hexylthiophene) (P3HT) as well as P3HT:fullerene bulk-heterojunction blends can be spin-coated from a mixture of the crystallizable solvent 1,3,5-trichlorobenzene (TCB) and a second carrier solvent such as chlorobenzene. Solidification is initiated by growth of macroscopic TCB spherulites followed by epitaxial crystallization of P3HT on TCB crystals. Subsequent sublimation of TCB leaves behind a replica of the original TCB spherulites. Thus, highly ordered thin films are obtained, which feature square-centimeter-sized domains that are composed of one spherulite-like structure each. A combination of optical microscopy and polarized photoluminescence spectroscopy reveals radial alignment of the polymer backbone in case of P3HT, whereas P3HT:fullerene blends display a tangential orientation with respect to the center of spherulite-like structures. Moreover, grazing-incidence wide-angle X-ray scattering reveals an increased relative degree of crystallinity and predominantly flat-on conformation of P3HT crystallites in the blend. The use of other processing methods such as dip-coating is also feasible and offers uniaxial orientation of the macromolecule. Finally, the applicability of this method to a variety of other semi-crystalline conjugated polymer systems is established. Those include other poly(3-alkylthiophene)s, two polyfluorenes, the low band-gap polymer PCPDTBT, a diketopyrrolopyrrole (DPP) small molecule as well as a number of polymer:fullerene and polymer:polymer blends. Macroscopic spherulite-like structures of the conjugated polymer poly(3-hexylthiophene) (P3HT) grow directly during spin-coating. This is achieved by processing P3HT or P3HT:fullerene bulk heterojunction blends from a mixture of the crystallizable solvent 1,3,5-trichlorobenzene and a second carrier solvent such as chlorobenzene. Epitaxial growth of the polymer on solidified solvent crystals gives rise to circular-symmetric, spherulite-like structures that feature a high degree of anisotropy.

The location of Ti atom in sodium alanate : an ab initio spin-polarised study

In this work, ab initio spin-polarised Density Functional Theory (DFT) calculations are performed to study the interaction of a Ti atom with a NaAlH4(001) surface. We confirm that an interstitially located Ti atom in the NaAlH4 subsurface is the most energetically favoured configuration as recently reported (Chem. Comm. (17) 2006, 1822). On the NaAlH4(001) surface, the Ti atom is most stable when adsorbed between two sodium atoms with an AlH4 unit beneath. A Ti atom on top of an Al atom is also found to be an important structure at low temperatures. The diffusion of Ti from the Al-top site to the Na-bridging site has a low activation barrier of 0.20 eV and may be activated at the experimental temperatures (∼323 K). The diffusion of a Ti atom into the energetically favoured subsurface interstitial site occurs via the Na-bridging surface site and is essentially barrierless.

Group 14 element-based non-centrosymmetric quantum spin hall insulators with large bulk gap

To date, a number of two-dimensional (2D) topological insulators (TIs) have been realized in Group 14 elemental honeycomb lattices, but all are inversionsymmetric. Here, based on first-principles calculations, we predict a new family of 2D inversion-asymmetric TIs with sizeable bulk gaps from 105 meV to 284 meV, in X2–GeSn (X = H, F, Cl, Br, I) monolayers, making them in principle suitable for room-temperature applications. The nontrivial topological characteristics of inverted band orders are identified in pristine X2–GeSn with X = (F, Cl, Br, I), whereas H2–GeSn undergoes a nontrivial band inversion at 8% lattice expansion. Topologically protected edge states are identified in X2–GeSn with X = (F, Cl, Br, I), as well as in strained H2–GeSn. More importantly, the edges of these systems, which exhibit single-Dirac-cone characteristics located exactly in the middle of their bulk band gaps, are ideal for dissipationless transport. Thus, Group 14 elemental honeycomb lattices provide a fascinating playground for the manipulation of quantum states.

Spin it to win it: A comparison of constraints-led versus traditional coaching approaches

This thesis aimed to compare the effects of constraints-led and traditional coaching approaches on young cricket spin bowlers, with a specific research focus on increasing spin rates (i.e., Revolutions per Minute). Participants were 22 spin bowlers from either an Australia state youth squad or an academy in England. Results indicate that adopting a constraints-led approach can benefit younger, inexperienced bowlers, whilst a traditional approach may assist more skilled, older bowlers. The findings are discussed with regards to how they may inform the learning design of training programs by cricket coaches.

On the zeros of the Abelian integrals for a class of Liénard systems

A planar polynomial differential system has a finite number of limit cycles. However, finding the upper bound of the number of limit cycles is an open problem for the general nonlinear dynamical systems. In this paper, we investigated a class of Liénard systems of the form x'=y, y'=f(x)+y g(x) with deg f=5 and deg g=4. We proved that the related elliptic integrals of the Liénard systems have at most three zeros including multiple zeros, which implies that the number of limit cycles bifurcated from the periodic orbits of the unperturbed system is less than or equal to 3.