The nuclear shielding and spin-spin coupling constants of (119)Sn in stannane, tetramethylstannane, methyltin halides Me4-nSnXn (X = Cl, Br, I; n = 1-3), tin halides, and some stannyl cations have been investigated computationally by DFT methods and Slater all-electron basis sets, including relativistic effects by means of the zeroth order regular approximation (ZORA) method up to spin-orbit coupling. Calculated (119)Sn chemical shifts generally correlate well with experimental values, except when several heavy halogen atoms, especially iodine, are bound to tin. In such cases, calculated chemical shifts are almost constant at the scalar (spin-free) ZORA level; only at the spin-orbit level is a good correlation, which holds for all compounds examined, attained. A remarkable "heavy-atom effect", analogous to that observed for analogous alkyl halides, is evident. The chemical shift of the putative stannyl cation (SnH3(+)) has also been examined, and it is concluded that the spectrum of the species obtained in superacids is inconsistent with a simple SnH3(+) structure; strong coordination to even weak nucleophiles such as FSO3H leads to a very satisfactory agreement. On the contrary, the calculated (119)Sn chemical shift of the trimesitylstannyl cation is in very good agreement with the experimental value. Coupling constants between (119)Sn and halogen nuclei are also well-modeled in general (taking into account the large uncertainties in the experimental values); relativistic spin-orbit effects are again quite evident. Couplings to (13)C and (1)H also fall, on the average, on the same correlation line, but individual values show a significant deviation from the expected unit slope.

A ZSM-5 fragment, containing 52 tetrahedral moieties, each of them formed by one silicon or one aluminum atom surrounded by four oxygen atoms, was employed to model (52T systems) by quantum chemical calculations (i) the influence of the positions of the acidic sites on the energetics of 22 aluminum monosubstituted and bisubstituted 52T acidic zeolite (H−ZSM-5) systems and (ii) the local adsorption properties and acidic strength of the corresponding −OH sites. The energetics and the structural properties of simpler acid H−ZSM-5 systems containing only five tetrahedral moieties (5T systems) were also modeled for comparison. B3LYP/6-31G(d,p) partial geometry optimization routines were performed on the 5T and 52T systems. On the latter, ONIOM(B3LYP/6-31G(d,p)|AM1) calculations and an alternative approach, i.e., the ONIOM method followed by a single-point at the above B3LYP/6-31G(d,p) level, aimed to decrease the need of computational resources, were also employed to analyze the properties of the different H−ZSM-5 models. The whole results showed that the orientation and the position of the acidic hydrogen atoms within the zeolite channel strongly affect the stability of the model systems, irrespective of the starting local topology characterizing the Al ↔ Si substitution site. Brönsted gas-phase acidity strength and adsorption-ability were evaluated through the analysis of the energy involved in (i) the proton dissociation from the acidic sites and (ii) the cis-but-2-ene and trans-but-2-ene adsorption on the same acidic sites. Both were affected, although to a very different extent, by the location and number of the considered −OH acidic groups. In particular, 2 among the 12 modeled acidic sites resulted in a highly stabilized zeolite structure, pointing out that the Al ↔ Si substitutions in the synthesis of aluminated ZSM-5 zeolites, and hence the corresponding catalytic activity, could preferentially occur on special sites. The choice of the computational method along with the size and the cutoff of the mimicked structures influenced the reliability of the calculations. The suggested alternative approach (that is, the ONIOM followed by the DFT single-point calculation) provided reasonable findings at very low computational cost.

We report the synthesis and characterization of dimeric viologen salts (1',1''-(alkane-1,n-diyl)bis(1-ethyl-4,4'-bipyridinium) with n = 4-10) with bis(trifluoromethanesulfonyl)amide (bistriflimide, Tf(2)N(-)) as a counteranion. For n = 4, 5 and 6, and for the nonylviologen cation (1,1'-dinonyl-4,4'-bipyridinium) we also prepared salts with the totally inorganic dodecatungstosilicate anion, SiW(12)O(40)(4-), featuring a poly-charged surface and nanosized dimensions. The materials have been characterized by means of calorimetric techniques, X-ray diffraction and solid state NMR and a comparison is made with analogous monomeric viologen salts exhibiting smectic mesophases. A strong odd-even effect is observed in the melting points and in the thermal behaviour of the bistriflimide dimeric systems, similar to what was reported for dipolar calamitic liquid crystal dimers, although the studied viologen dimers are not mesomorphic. By increasing the size of the counteranion we have observed a destabilization of the crystal phases and of the mesophases in favour of a glassy amorphous state. Implications on the design of novel ionic liquid crystals are discussed. The electrochemical behaviour in solution has been investigated by cyclic voltammetry measurements: interestingly, the odd-even effect is clearly visible also in the redox potentials. The spin-pairing of the viologen radical cations formed at each end of the dimer is responsible for the observed redox trend. Insights on the structure of the spin-paired dimer have been obtained by DFT calculations.

The stability of thermotropic ionic liquid crystals is essentially due to micro-phase segregation between the ionic heads and the long alkyl chains. Here we show, using newly synthesized viologen dimers, that the structure of the central core is another key parameter to play with in order to tune the mesomorphic behaviour.

We have investigated, using dispersion corrected DFT methods, the structure and the spectroscopic properties of carbon buckyonions C60@C180 and C60@C240. C60, C180 and C240 showed a noticeable variation of their geometries in C60@C180 and C60@C240, upon encapsulation. Inclusion of the dispersion correction term in the calculations has a significant effect on the geometry. C60@C180 has a large positive interaction energy, while for C60@C240 a negative value is found indicating that only C240 can easily accommodate C60. In both cases dispersion interactions strongly contribute to the stabilization of the complexes. Vibrational frequencies, electronic transitions and NMR properties have been computed. The results show that encapsulation leads to appreciable variation in the characteristic resonances thus offering a useful tool for a spectroscopic identification of these species.

Non-symmetric alkyl/polyfluoroalkyl viologens with electrochromism in the smectic phase and mesomorphism of bent core oxadiazolyl viologens with hampered electrochromism.

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We have tested several computational protocols, at the nonrelativistic DFT level of theory, for the calculation of 1J(119Sn, 13C) and 2J(119Sn, 1H) spin-spin coupling constants in di- and trimethyltin(IV) derivatives with various ligands. Quite a good agreement with experimental data has been found with several hybrid functionals and a double-zeta basis set for a set of molecules comprising tetra-, penta-, and hexa-coordinated tin(IV). Then, some of the protocols have been applied to the calculation of the 2J(119Sn, 1H) of the aquodimethyltin(IV) ion and dimethyltin(IV) complex with D-ribonic acid and to the calculation of 1J(119Sn, 13C) and 2J(119Sn, 1H) of the dimethyltin(IV)-glycylglycine and glycylhistidine complexes in water solutions. Solvent effects have been considered in these cases by including explicit water molecules and/or the solvent reaction field, resulting in a good agreement with experimental data. The proposed protocols constitute a helpful tool for the structural determination of di- and triorganotin(IV) derivatives.