Engineering a remarkably low HOMO-LUMO gap by covalent linkage of a strong pi-donor and a pi-acceptor--tetrathiafulvalene-sigma-polynitrofluorene diads: their amphoteric redox behavior,electron transfer and spectroscopic properties

Novel R3TTF-sigma-A compounds 14, 16 and 19 (R3TTF = trial-kyletrathiafulvalene, sigma = saturated spacer, A = polynitrofluoren-9-dicyano-methylene acceptor) incorporating very strong donor and acceptor moieties have been synthesized by condensation of the corresponding R3TTF-sigma-fluoren-9-one diads with malononitrile. Reversible five-step amphoteric redox behavior has been observed with an extremely low HOMO-LUMO gap (approximately 0.3 eV). For compound 14 a strong EPR signal is observed in the solid state, ascribed to intermolecular complexation: a less intense signal is seen in solution, corresponding to ca. 2% of the molecules existing in a radical form at room temperature. Intramolecular charge transfer in diads 14 and 16 is manifested in strong absorption bands in the near-IR region of their electronic spectra. Spectroelectrochemical data reveal marked electrochromic behavior in the visible and near-IR region of both compounds. The first X-ray crystal structure of a fluorene radical-anion salt is reported, namely the copper salt of 2,4,5,7-tetranitro-9- dicyanomethylenefluorene (1:1 stoichiometry).     

Formation and Depth Profiling Analysis of Multilayers Derived from Sol-Gel Processing Using Dynamic SIMS, RBS, and TEM

Silica sol-gel single layer AR coatings are used in high peak power pulsed lasers due to their high laser induced damage threshold (LIDT) and their low refractive index (1.22). We have used sol-gel processing to spin and dip coat multilayers of alternating high index (zirconia/hafnia) and low index (base catalysed silica) sol-gels on to fused silica substrates. When tailored at the correct thickness these stacks have shown >95% reflectivity at 355 nm and normal incidence whilst retaining a high LIDT. Depth profiling using Dynamic Secondary Ion Mass Spectrometry (DSIMS) and Rutherford back scattering (RBS) through these multilayer coatings has revealed the effect of increasing the number of layers in the stack. Results are presented for both spin and dip coated multilayers and a significant difference in the interfacial boundary is seen between the two coating processes. These differences are related to changes in the LIDT of the coatings. Individual layer thicknesses were estimated using this technique and compared to values gained from UV-Visible spectroscopy. TEM analysis of an ion-milled cross-section of the multilayers was performed showing the colloidal silica coatings and the depth of interpenetration of the interfaces.     

Slow magnetic dynamics in the Ni10 family of compounds

We report on a family of molecular crystals containing non-interacting Ni₁₀ magnetic molecules. These crystals display slow relaxation of the magnetization below a temperature as high as 17 K. This behavior is not associated with an anisotropy energy barrier. The magnetic energy spectrum of a Ni₁₀ molecule is structured in dense well-separated bands, the lowest of which makes the crystal nearly opaque to phonons of energy below about 1 meV. We interpret the observed non-equilibrium behavior as due to resonant trapping of these low-energy phonons.     

A high-nuclearity, beyond "fully reduced" polyoxo(alkoxo)vanadium(III/IV) cage

The solvothermal synthesis, crystal structure and preliminary magnetic studies are reported of the first high nuclearity V(III)-based polyoxo(alkoxo)vanadium cage, a V(III)16V(IV)2 complex.     

High-temperature slow relaxation of the magnetization in Ni10 magnetic molecules

We investigate a family of molecular crystals containing noninteracting Ni10 magnetic molecules. We find slow relaxation of the magnetization below a temperature as high as 17 K and we show that this behavior is not associated with an anisotropy energy barrier. Ni10 has a characteristic magnetic energy spectrum structured in dense bands, the lowest of which makes the crystal opaque to phonons of energy below about 1 meV. We ascribe the nonequilibrium behavior to the resulting resonant trapping of these low-energy phonons. Trapping breaks up spin relaxation paths leading to a novel kind of slow magnetic dynamics which occurs in the lack of anisotropy, magnetic interactions and quenched disorder.     

Structural consequences of the one-electron reduction of d4 [Mo(CO)2(eta-PhC[triple bond]CPh)Tp']+ and the electronic structure of the d5 radicals [M(CO)L(eta-MeC[triple bond]CMe)Tp'] {L = CO and P(OCH2)3CEt}

Reduction of [M(CO)2(eta-RC[triple bond]CR')Tp']X {Tp' = hydrotris(3,5-dimethylpyrazolyl)borate, M = Mo, X = [PF6]-, R = R' = Ph, C6H4OMe-4 or Me; R = Ph, R' = H; M = W, X = [BF4]-, R = R' = Ph or Me; R = Ph, R' = H} with [Co(eta-C5H5)2] gave paramagnetic [M(CO)2(eta-RC[triple bond]CR')Tp'], characterised by IR and ESR spectroscopy. X-Ray structural studies on the redox pair [Mo(CO)2(eta-PhC[triple bond]CPh)Tp'] and [Mo(CO)2(eta-PhC[triple bond]CPh)Tp'][PF6] showed that oxidation is accompanied by a lengthening of the C[triple bond]C bond and shortening of the Mo-C(alkyne) bonds, consistent with removal of an electron from an orbital antibonding with respect to the Mo-alkyne bond, and with conversion of the alkyne from a three- to a four-electron donor. Reduction of [Mo(CO)(NCMe)(eta-MeC[triple bond]CMe)Tp'][PF6] with [Co(eta-C5H5)2] in CH2Cl2 gives [MoCl(CO)(eta-MeC[triple bond]CMe)Tp'], via nitrile substitution in [Mo(CO)(NCMe)(eta-MeC[triple bond]CMe)Tp'], whereas a similar reaction with [M(CO){P(OCH2)3CEt}(eta-MeC[triple bond]CMe)Tp']+ (M = Mo or W) gives the phosphite-containing radicals [M(CO){P(OCH2)3CEt}(eta-MeC[triple bond]CMe)Tp']. ESR spectroscopic studies and DFT calculations on [M(CO)L(eta-MeC[triple bond]CMe)Tp'] {M = Mo or W, L = CO or P(OCH2)3CEt} show the SOMO of the neutral d5 species (the LUMO of the d4 cations) to be largely d(yz) in character although much more delocalised in the W complexes. Non-coincidence effects between the g and metal hyperfine matrices in the Mo spectra indicate hybridisation of the metal d-orbitals in the SOMO, consistent with a rotation of the coordinated alkyne about the M-C2 axis.