An exceptional red shift of emission maxima upon fluorine substitution

The effect of perfluorination on photophysical properties was investigated through synthesis and photophysical characterization of two isostructural donor-acceptor-donor dye molecules. The synthesis of two versatile fluorinated benzene compounds, 1,4-difluoro-2,5-diperfluorooctylbenzene (1) and 1,4-dibromo-2,5-difluoro-3,6-diperfluorooctylbenzene (2), is presented. The X-ray structure of 2 has been determined and shows that the perfluorinated octyl chains segregate from the benzene rings in the solid state, giving rise to a layered structure. The further synthesis through Suzuki coupling reactions using 4-formylbenzeneboronic acid with (2) and 1,4-dibromo-2,5-dioctylbenzene (3) gave, respectively, 1,4' '-diformyl-2',5'-difluoro-3',6'-diperfluorooctyl-p-terphenylene (4) and 1,4' '-diformyl-2',5'-dioctyl-p-terphenylene (5). The condensation of the dialdehydes 4 and 5 with 9,10-phenanthrenequinone and ammoniumbicarbonate in glacial acetic acid gave the dye molecules 1,4' '-bis(1H-phenanthro[9,10-d]imidazol-2-yl)-2',5'-difluoro-3',6'-diperfluorooctyl-p-terphenylene (6) and 1,4' '-bis(1H-phenanthro[9,10-d]imidazol-2-yl)-2',5'-dioctyl-p-terphenylene (7), respectively. The UV-vis spectra of the two molecules are nearly identical, whereas the fluorescence spectra are very different. Compound 7 shows blue fluorescence with little solvent dependence (lambda(emission) = 410 nm in THF, CH2Cl2, and hexane), whereas compound 6 shows a highly solvent-dependent emission wavelength (lambda(emission) = 583 nm in THF, lambda(emission) = 560 nm in CH2Cl2, and lambda(emission) = 450 nm in hexane). The fluorescence red shift of compound 6 in a series of solvents with different polarity is discussed using the Lippert-Mataga equation. Fluorescence lifetime and quantum yields were also determined. Ultraviolet photoelectron spectroscopy (UPS) was performed on thin films of compound 6 and 7 on a gold substrate. The observed ionization potential was 6.15 eV for 6 and 5.85 eV for 7" [correction].     

Synthesis and application of chiral phosphino-imidazoline ligands: Ir-catalyzed enantioselective hydrogenation

[reaction: see text] A series of chiral phosphino-imidazolines (PHIM ligands) 1a-j with different substituents at the stereogenic center, the nitrogen atom of the imidazoline ring, and at the phosphorus atom were synthesized. Iridium complexes derived from these ligands have been evaluated as catalysts for the enantioselective hydrogenation of unfunctionalized olefins. In several cases, higher enantiomeric excesses were observed than with analogous phosphino-oxazoline ligands.     

Stepwise and directional synthesis of end-functionalized single-oligomer OPVs and their application in organic solar cells

A new stepwise directional synthetic route to single-oligomer p-phenylenevinylenes (OPVs) has been developed. The first step in the reaction sequence is the condensation of a functionalized benzaldehyde with a novel monomer having a methyl phosphonate ester group in one end and an acetal-protected aldehyde at the other end of a stilbene core. Oligomerization then proceeds stepwise by alternating reaction of the previous aldehyde-terminated OPV fragment with the monomer and deprotection of the acetal. Thus, a series of OPVs with 3, 5, 7, 9, and 11 phenylene vinylene units has been prepared that has an electron-donating methoxy group at one end and an electron-accepting aldehyde group at the other end. Some examples where a dimethylamino group replaced the methoxy group were also prepared. The oligomer with seven phenylene vinylene units was then further derivatized at the aldehyde position to create a series of OPVs with a range of substituents from strongly electron-accepting nitrophenyl to electron-donating methoxyphenyl. Photovoltaic cells were assembled with the synthesized OPVs as the photoactive layer. Illumination under simulated sunlight (AM1.5) gave short circuit currents (Isc) in the range 0.015-0.5 mA cm(-2) and typical open circuit voltages (Voc) of 0.4-0.8 V. The maximum efficiency obtained was approximately 0.1%.     

Fluorinated molecules relevant to conducting polymer research

The synthesis of versatile fluorine compounds for conducting polymer research on fluorinated materials is presented. 1,2,4,5-Tetrafluorobenzene was converted to 1,2,4,5-tetrafluorobenzaldehyde (1) and protected as an acetal. This gave the acetals 1,2,4,5-tetrafluoro-3-(1,3-dioxol-2-yl)benzene (2a) and 1,2,4,5-tetrafluoro-3-(5,5-dimethyl-1,3-dioxan-2-yl)benzene (2b). Compounds 2a and 2b were converted into the semiprotected 2,3,5,6-tetrafluoroterephthaldehydes: 1,2,4,5-tetrafluoro-3-(1,3-dioxol-2-yl)-6-formylbenzene (3a) and 1,2,4,5-tetrafluoro-3-(5,5-dimethyl-1,3-dioxan-2-yl)-6-formylbenzene (3b). While 3a was easily deprotected to give 2,3,5,6-tetrafluoroterephthaldehyde (4) compound 3b proved very resilient to hydrolysis and gave a 1:1 mixture of 4 and 1,2,4,5-tetrafluoro-3,6-bis(5,5-dimethyl-1,3-dioxan-2-yl)benzene (5). Compound 4 was reduced to 1,2,4,5-tetrafluoro-3,6-dihydroxymethylbenzene (6) and converted into 1,2,4,5-tetrafluoro-3,6-dibromomethylbenzene (7). Compound 7 was finally converted into 1,2,4,5-tetrafluoro-3,6-bis(diethylphosponylmethyl)benzene (8). Compounds 4 and 8 are versatile fluorinated molecules that can be used to replace their hydrogen counterparts in many molecules and materials. To illustrate this compounds 4 and 8 were oligomerised to give partially fluorinated polyphenylenevinylene (9).     

Relationship between soil organic C degradability and the evolution of the delta13C signature in profiles under permanent grassland

The main objective of this research was to investigate to what extent the potential C dynamics of soil organic matter (SOM) are related to the degree of 13C enrichment with increasing depth in soil profiles under permanent grassland. The evolution of the C content and the 13C natural abundance (delta13C value) of SOM were investigated in three soil profiles (0-40 cm depth) under permanent grassland of varying texture (a loamy sand, a loam and a clay loam soil). The delta13C value of the SOM showed a gradual increase with increasing depth and decreasing C content in the profiles, ranging from 1.9 per thousand (loamy sand soil), 2.9 per thousand (clay loam soil) and 4 per thousand (loam soil) in relation to the delta13C value of SOM at the surface. The relationship between the 13C enrichment and total organic C content at different depths in the profiles (down to 40 cm depth in the loam and clay loam soil, down to 25 cm depth in the loamy sand soil) could be well described by the Rayleigh equation. The enrichment factors epsilon, associated with the Rayleigh approximation of the data, ranged from -1.57 per thousand (clay loam soil) to -1.64 per thousand (loamy sand soil) and -1.91 per thousand (loam soil). The potential C dynamics in four depth intervals from the profiles (0-10, 10-20, 20-30 and 30-40 cm depth) were determined by means of an incubation experiment. The C decomposition rate constants from the four sampling depths in the profiles showed a significant, positive correlation (y = 0.21x + 0.018, R(2) = 0.66, p < 0.005) with the corresponding Deltadelta13C values (change of the delta13C value per depth increment). A better correlation was obtained when only the data from the upper 20 cm in the profiles (y = 0.21x + 0.019, R(2) = 0.78, p < 0.05) were considered. These results suggest that the Deltadelta13C values in the surface layers of profiles under permanent grassland may serve as an indicator of the potential degradability or the stability of the SOM (in terms of C decomposition rate constants).     

Evolution of the delta13C signature related to total carbon contents and carbon decomposition rate constants in a soil profile under grassland

Evolution of the total carbon (C) content and the (13)C enrichment (delta(13)C signature) of soil organic matter (SOM) with increasing depth in a soil profile under permanent grassland (C(3) vegetation) were investigated. The relationship between the total C content and the delta(13)C signature at different depths in the upper 30 cm of the soil profile could be well fitted by the Rayleigh equation (y = -29.8 - 2.3x, R(2) = 0.95, p < 0.001), describing the enrichment in (13)C as resulting from isotopic fractionation associated with C mineralization (isotope enrichment factor epsilon = -2.3 per thousand). Potential C dynamics of SOM in four depth intervals of the profile (0-10, 10-20, 20-30 and 30-40 cm depth) were investigated through an incubation study. The C decomposition rate constants decreased with increasing sampling depth from 0.0479 yr(-1) (0-10 cm sampling depth) to 0.0256 yr(-1) (30-40 cm sampling depth) and were highly correlated (y = 0.02 + 0.13x, R(2) = 0.93, p < 0.05) with the corresponding deltadelta(13)C values (average change of the delta(13)C signature per depth increment). These results suggest that changes of the delta(13)C signature of SOM in undisturbed soil profiles under continuous C(3) vegetation may serve as an indicator of the variation of SOM quality with increasing depth.     

Special metrics and triality

We investigate a new 8-dimensional Riemannian geometry defined by a generic closed and coclosed 3-form with stabiliser PSU(3), and which arises as a critical point of Hitchin's variational principle. We give a Riemannian characterisation of this structure in terms of invariant spinor-valued 1-forms, which are harmonic with respect to the twisted Dirac operator ? on Δ⊗Λ¹. We establish various obstructions to the existence of topological reductions to PSU(3). For compact manifolds, we also give sufficient conditions for topological PSU(3)-structures that can be lifted to topological SU(3)-structures. We also construct the first known compact example of an integrable non-symmetric PSU(3)-structure. In the same vein, we give a new Riemannian characterisation for topological quaternionic Kähler structures which are defined by an Sp(1)⋅Sp(2)-invariant self-dual 4-form. Again, we show that this form is closed if and only if the corresponding spinor-valued 1-form is harmonic for ? and that these equivalent conditions produce constraints on the Ricci tensor.     

Morphological control and molecular recognition by bis-urea hydrogen bonding in micelles of amphiphilic tri-block copolymers

Hydrogen bonding between urea groups of amphiphilic tri-block copolymers considerably affects their self-assembly in water, which results in a strong modification of morphology and viscosity of aqueous solutions; the hydrogen bonding motif in these amphiphilic copolymers allows molecular recognition of small molecules with complementary hydrogen bonding units.