On assignment of fundamental vibrational modes of hypophosphite anion and its deuterated analogue

Results of ab initio and density functional theory calculations on the structure and vibrational frequencies of hypophosphite anion indicate earlier experimental assignments of the fundamental vibrational modes are correct while the recent reassignments of several modes proposed by Bickley et al. are inconsistent with the calculated results.     

Intermolecular coupling in nanometric domains of light-harvesting dendrimer films studied by photoluminescence near-field scanning optical microscopy (PL NSOM)

Near-field scanning optical microscopy (NSOM) has been used to investigate the photophysical characteristics of first- to fourth-generation (G1 to G4) light-harvesting dendrimer thin films containing coumarin-343 and coumarin-2 as the core and peripheral chromophores, respectively. Thin film photoluminescence (PL) spectra exhibit a significant red shift in the lower generations (G1, G2, and G3) as compared to their respective solution PL spectra, implying the formation of excimers. Spatially resolved PL NSOM images exhibit pronounced nanoscopic domains in G1, which become more homogeneous in higher generations due to site-isolation of the core chromophore. G4 exhibits complete site-isolation for these light-harvesting dendrimer films.     

Role of surface crossings in the photochemistry of nitromethane

The photodissociation dynamics of nitromethane (CH(3)NO(2)) starting at the S(3) excited state has been studied at the complete active space self-consistent field level of theory in conjunction with atomic natural orbital type basis sets. In addition, the energies of all the critical points and the energy profiles connecting them have been recomputed with the multiconfigurational second-order perturbation method. It is found that the key step in the reaction mechanism is a radiationless decay through an S(3)S(2) conical intersection. The branching space spanned by the gradient difference and nonadiabatic coupling vectors of this crossing point comprises dissociation into excited nitromethane plus singlet atomic oxygen [CH(3)NO(1A")+O((1)D)] and S(3)-->S(2) deactivation, respectively. Furthermore, deactivated nitromethane S(n (n<3)) can decompose in subsequent steps into CH(3)+NO(2), where NO(2) is generated at least in two different electronic states (1 (2)B(2) and 1 (2)A(1)). It is shown that formation of excited nitric oxide NO(A (2)Sigma) arises from CH(3)NO(1A") generated in the previous step. In addition, four crossings between singlet and triplet states are localized; however, no evidence is found for a relevant role of such crossings in the photochemistry of CH(3)NO(2) initiated at S(3) state in the gas phase.     

Chiral induction in self-assembled helicates: CHIRAGEN type ligands with ferrocene bridging units

The aim of this work was the preparation of enantiomerically pure bis(pinene-bipyridine) ligands containing the ferrocenyl moiety. Several such ligands (1-3) were synthesized and completely characterized. These molecules can be diastereoselectively deprotonated at the acidic methylene group of the pinene moiety using a strong and sterically hindered base such as LDA. Subsequent reaction of the formed anion with alkyl halides yield the family of C(2)-symmetric enantiopure compounds (1a-c). Copper(I), silver(I), or zinc(II) complexes with several ligands (C1-C8) were prepared and structurally characterized in the solid state and in solution. Self-assembled helical species are formed in several cases. It became evident that the chiral groups present in the ligand do not completely determined the helical configuration of the assemblages. Diastereoselectivity is thus not complete with this type of ligands, contrary to other, similar ligands studied before.     

An Assay for the Quantitation of Photofrin in Tissues and Fluids

A method for determining the concentration of Photofrin in tissues and biological fluids was developed. The procedure is based on the dissolution of biological material with Solvable a commercially available tissue so-lubilizer, followed by porphyrin-specific fluorescence detection and measurement. It was found necessary to use a quadratic standard curve for the estimation of unknown Photofrin concentrations. While this method is limited to compounds that are stable in strong base, it has the advantages of being sensitive, rapid and low cost .     

Deactivation of silica surfaces with a silanol-terminated polysiloxane; structural sharacterization by inverse gas chromatography and solid-state NMR

Retention gape deactivated with Silicone OV-1701-OH show good chromatographic performance and remarkable stability against water induced stationary phase degradrdation. In an attempt to better understand the findamentals off the deactivation process using silanol terminated polysiloxanes, a fumed silica was deactivated with Silicon OV-1701-OH. In contrast to fused silic capillaries, fumed silica (Aerosil A-200) can be studied by ²⁹Si cross-polarization magic-angle-spinning (CPMAS) NMR, thus serving as a model substrate for fused silica. Retention data from inverse gas chromatography at infinite dilurion and ²⁹Si CP MAS NMR data of five Aerosil phases, differing in residual silanol surface concentration, are correlated with the aim of validating this approach for stationary phase characterization. A comparatively detailed model of the deactivating polymer layer that explains the observed absorption activities is deduced. Surface silanols are shown to play a key role in the polymer layer, the structure of which is of primary importance for the absorption behavior after deactivation. Contrary to common belief, the absolute silanol surface concentration after deativation is only of secondary importance for the overall absorption activity. High silanol surface concentrations enhance degradation of the polysiloxane chains into small cyclic fragments as well as subsequent absorption and immobolization to the silica substrate surface. The mobility of linear polysiloxane chains in the kHz regime (as determined bby NMR cross-polarization dynamics) appears to determine the extent which the residual silanols are accessible for analytes. It is therefore anticipated that there is an optimum silanol surface concentration of fused silica surfaces to be deactivated with silanol terminated polysiloxanes; it should be lazrge enough to adsord polymer fragments, but not large to avoid excessive residual silanol activity.     

Ambient-pressure vapor deposition of octanethiol self-assembled monolayers

Scanning tunneling microscopy was used to characterize self-assembled monolayers (SAMs) of octanethiol on Au(111), created using vapor deposition at elevated temperatures and ambient pressure. Monolayers contained large, close-packed ( radical3 x radical3)R30 degrees domains with sizes considerably larger than those typically formed from conventional solution-phase preparation and with crystallographically straight domain boundaries. New striped surface phases were also observed, including a 13 x radical3 phase with a density that was 69% of the close-packed density; these striped phases appeared topographically higher in STM images than close-packed monolayers.     

Synthesis, structure, and X-band (9.5 GHz) EPR characterization of the new series of pH-sensitive spin probes: N,N-disubstituted 4-amino-2,2,5,5-tetramethyl-3-imidazoline 1-oxyls

[reaction: see text] An approach to the synthesis of new imidazoline nitroxides bearing an N',N'-disubstituted amidine group is reported. The approach is based on the alkylation of diamagnetic 4-R-amino-1,2,2,5,5-pentamethyl-3-imidazolines with bromoacetic acid ethyl ester; the products of alkylation are further oxidized to the corresponding nitroxides. The approach allows a variety of functional groups to be introduced into the nitroxide molecule structure. Alkylation with bromoacetic acid ethyl ester was found to proceed with high regioselectivity and afford the products of exo-alkylation. The regiochemical assignment is made on the basis of 13C NMR spectra and confirmed by X-ray diffraction study. All of the nitroxides synthesized here were shown to have pH-dependent EPR spectra with pKa ranging from 3.5 to 6.2. For nitroxides 13 bearing the carboxylic group remote to the nitroxide moiety, the changes in isotropic magnetic parameters of EPR spectra due to reversible deprotonation of the carboxylic group were found to be small. For these nitroxides, we demonstrate an alternative approach for pKa determination that is based on measuring the peak-to-peak line width of the EPR spectrum in the presence of the paramagnetic broadening agent potassium ferricyanide. The partition coefficients of nitroxides in octanol/H2O and octanol/phosphate buffer solution mixtures were measured to reveal a range of their lipophilicities.     

Does alpha-fluorination affect the structural trans-influence and kinetic trans-effect of an alkyl ligand? Molecular structures of Pd(TMEDA)(CH(3))(R(F)) and a kinetic study of the trans to cis isomerization of Pt(TMEDA)(CH(3))(2)I(R(F)) [R(F) = CF(2)CF(3), CFHCF(3), CH(2)CF(3)

Reaction of Pd(TMEDA)(CH(3))(2) [TMEDA = tetramethylethylenediamine] with fluoroalkyl iodides R(F)I affords a series of square planar Pd(II) complexes Pd(TMEDA)(CH(3))(R(F)) [R(F) = CF(2)CF(3) (9), CFHCF(3) (10), CH(2)CF(3) (11)], presumably by oxidative addition followed by reductive elimination of CH(3)I. The solid-state structures of each compound have been determined by single crystal X-ray diffraction studies, allowing the effect of increasing alpha-fluorination on the structural trans-influence of alkyl ligands to be examined. In these compounds there is no significant difference observed in the trans-influence of the three fluorinated alkyl ligands toward the trans-N atom, although a significant cis-influence on the neighboring methyl ligand is apparent. Oxidative addition of the same series of fluoroalkyl ligands to the corresponding Pt(TMEDA)(CH(3))(2) affords octahedral Pt(IV) complexes trans-Pt(TMEDA)(CH(3))(2)(R(F))I [R(F) = CF(2)CF(3) (12), CFHCF(3) (13), CH(2)CF(3) (14)] as the kinetic products. In each case, subsequent isomerization to the corresponding all cis-isomers is observed; in the case of 13, the stereocenter at the alpha-carbon results in two diastereomeric cis-isomers, which are formed at different rates. The molecular structures of 13 and its more stable all cis-isomer 16b have been crystallographically determined. Kinetic studies of the trans-cis isomerization reactions show the mechanism to involve a polar transition state, presumably involving iodide dissociation, followed by rearrangement of the cation, and iodide recombination. High dielectric solvents increase the rate, but solvent coordinating ability has no effect. Dissolved salts (LiI, LiOTf) show normal accelerative salt effects, with no inhibition in the case of added iodide, consistent with the formation of an intimate ion pair intermediate. The kinetic parameters show that the trans-effects of fluoroalkyl ligands in these compounds follow the order expected from the relative sigma-donor properties of the ligands, with CF(2)CF(3) < CFHCF(3) < CH(2)CF(3).