Synthesis and immobilization of molecular switches onto titaniumdioxide nanowires

The precursor [Fe^III(L)Cl (L = N,N′-bis(2′-hydroxy-3′-methyl-benzyliden)-1,7-diamino-4-azaheptane) is combined with [Mo(CN)₈]^4? yields a star shaped nona-nuclear cluster, [Mo^IV{(CN)Fe^III(L)}₈]Cl₄. This Fe₈Mo molecule is a high-spin system at room temperature. On cooling to 20 K some of the iron(III) centres in the molybdenum(IV)-star switch to the low-spin state as proven by Mössbauer spectroscopy. This molecule was deposited on TiO₂ nanowires by electrostatic interactions between the cluster cations and the surface functionalized titanium oxide nanowire. The synthesis and surface binding of the multistable molecular switch was demonstrated using IR and UV–Vis spectroscopy (high-resolution) transmission electron microscopy ((HR)TEM) and Mössbauer spectroscopy. High- and low-temperature Mössbauer spectra indicate that the spin state transition of the free cluster molecules is preserved after surface binding. The above results emphasize the possibility of fabricating molecule-based low-dimensional structures by using traditional bottom-up approaches based on the electrostatic interaction between the cluster cations and polymer functionalized nanowires. These results can be generalized for the application to both charged and non-charged molecules.     

Syndiotactic‐specific radical polymerization of N,N‐dimethylacrylamide in the presence of tartrates: A proposed mechanism for the polymerization

Radical polymerization of N,N‐dimethylacrylamide (DMAAm) was investigated in the presence of tartrates, such as diethyl L ‐tartrate, diisopropyl L ‐tartrate, and di‐n‐butyl L ‐tartrate, in toluene at low temperatures. Syndiotactic polymers were obtained in the presence of tartrates, whereas isotactic polymers were obtained in the absence of tartrates. The syndiotactic‐specificity increased with increasing amount of tartrates and with decreasing polymerization temperature. NMR analysis suggested that DMAAm and tartrates formed a 1:1 complex through double hydrogen bonding. A mechanism for the syndiotactic‐specific radical polymerization of DMAAm is proposed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1192–1203, 2009     

The effect of the N‐substituent s‐trans to the carbonyl group of N‐methylacrylamide derivatives on the stereospecificity of radical polymerizations

Radical polymerization of N‐methylacrylamide (NMAAm), N,N‐dimethylacrylamide (DMAAm), and N‐methyl‐N‐phenylacrylamide (MPhAAm) was investigated in toluene at low temperatures. Atactic, isotactic, and syndiotactic polymers were obtained by the polymerization of NMAAm, DMAAm, and MPhAAm, respectively, indicating that the stereospecificity of the radical polymerization of acrylamide derivatives depended on the N‐substituents of the monomer used. From the viewpoint of monomer structure, the origin of the stereospecificity of radical polymerization of NMAAm derivatives is discussed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6534–6539, 2009     

Sensitivity of the NTB phase formation to the molecular structure of imino-linked dimers

ABSTRACT

Here we report on the synthesis and mesomorphic properties of a series of imino-linked dimeric molecules. In order to improve our understanding of the structure–N_TB phase correlations, we have studied the impact of geometric and electronic factors arising from varying mesogenic units, different spacer lengths and from the ratio (n/m) between the lengths of terminal chains (n) and spacer (m). From the perspective of the molecular geometry, the results show that the stability of the N_TB phase results from increasing effective molecular bending and with the broadening of the mesogenic unit, in particular near the spacer, and that the n/m ratio plays a substantial role in conjunction with the specific mesogenic unit. A computational study of the electronic properties shows that a broadening of the mesogenic core in the vicinity of the spacer is associated with an increased anisotropy of the electrostatic potential distribution. Within a given series of materials our study suggests that the incidence of the N_TB phase and its thermal stability are governed by the synergy of specific geometrical factors and the anisotropy of the electrostatic potential distribution of the mesogenic core.     

Quantification of the push-pull character of azo dyes and a basis for their evaluation as potential nonlinear optical materials

The push-pull characters of a large series of donor-acceptor substituted azo dyes—71 structures in all—have been quantified by the NN double bond lengths, d_NN, the ¹⁵N NMR chemical shift differences, Δδ_15N, of the two nitrogen atoms and the quotient, π^∗/π, of the occupations of the antibonding π^∗, and bonding π orbitals of this partial NN double bond. The excellent correlation of the occupation quotients with the bond lengths strongly infers that both π^∗/π and d_NN are excellent parameters for quantifying charge alternation in the push-pull chromophore and the molecular hyperpolarizability, β₀, of these compounds. By this approach, selected compounds can be appropriately considered as viable candidates for nonlinear optical (NLO) applications.     

Non-adiabatic dynamics of pyrrole: Dependence of deactivation mechanisms on the excitation energy

Non-adiabatic dynamics simulations were performed for pyrrole at time-dependent density functional theory level using the trajectory surface hopping approach. Initial conditions were prepared based on the UV-absorption spectrum so as to simulate monochromatic absorption in three distinct spectral regions. The results showed predominance of the NH-stretch mechanism for excited-state relaxation. With increasing initial energy, however, other mechanisms are activated as well, even though they still occurred for a minor fraction of the trajectories. Dynamics starting at the origin of the absorption spectrum exhibited internal conversion to the ground state with a time constant of 20 fs. In contrast, dynamics starting at higher energies gave rise to much longer time constants for internal conversion near 200 fs.     

Evidence for a biogenic, microorganismal origin of rock varnish from the Gangdese Belt of Tibet

In the present study we examined material from the Ashikule Basin of Tibet. Chemical analyses were performed by use of energy dispersive X-ray spectroscopy and electron probe microanalysis to clarify whether the varnish layers that had developed on the surface of the rhyolite are indeed composed of varnish bodies and silica glaze. Electron microscopic analyses revealed that the surface of the varnish is covered both by filamentous hyphae bacterial and cocci-shaped forms. Within the varnish mineral layer in those samples two forms of bacteria-like microorganisms exist; cocci as tightly packed bacterial aggregates [within varnish bodies], and bacillus-like microorganisms [within the varnish matrix, that surrounds the varnish bodies]. The bacillus-like forms are embedded in a network of filaments that have diameters between 35 and 45 nm. These bacilli with the surrounding filaments are assumed to have been involved in biofilm formation (synthesis of extracellular polymeric substances) prior to their live burial. We concluded that the formation of the varnish layers was for the most part biogenically driven by microorganisms.     

Solid-state photodimerization of 4-aryl-1,4-dihydropyridines studied by C CPMAS NMR spectroscopy

¹³C CPMAS NMR spectroscopy has been applied to monitor the solid-state reaction of two different photodimerizing 4-phenyl-1,4-dihydropyridines yielding a cage dimer in one case and an anti-dimer in the other case. The spectra of the reacting monomers exhibit a magnetical inequivalence of chemically equivalent CO and C2/4 carbon atoms caused by a rotation of the pseudoaxially oriented 4-phenyl substituent out off the plane through N1, C3, C8 which could be determined by X-ray crystal structure analyses of the centrosymmetrically arranged monomers. The ¹³C CPMAS NMR monitoring of the cage dimer formation proves that the reaction takes place in two steps via a syn-dimer for which a non-symmetrical structure was derived from the spectrum. The non-symmetrical structure was confirmed by X-ray crystal structure analysis of one structurally related derivative. A centrosymmetric structure for both the finally formed cage dimer and the anti-dimer of the other monitored photoreaction was proved by their spectra with one set of signals for each half of the dimers, respectively. Thus, conformational properties of the molecules as well as the symmetry of the products can be directly derived from the ¹³C CPMAS NMR spectra.