Heterocyclic derivatives of naphthalene-1,8-dicarboxylic anhydride. Part I. Nitro-7H-benzimidazo[2,1-a]benz[de]isoquinolin-7-ones

Condensation of o-phenylenediamine with 2-, 3- and 4-nitronaphthalene-1,8-dicarboxylic anhydrides gives, in each case, an isomer mixture. Separation of the mixtures into the six isomeric mononitro-7H-benzimidazo[2,1-a]benz[de]isoquinolin-7-ones is described and the isomers characterised in respect of previously reported data on some isomers; ir and mass spectrum data are reported, the latter showing fragmentation ions which may be used in characterising dyes based on this chromophore. Other new derivatives of 7H-benzimidazo[2,1-a]benz[de]isoquinolin-7-one are also described.     

Interannular communication in the radical anions of bis-cyclooctatetraene systems

[reaction: see text] The room-temperature potassium reduction of 1,2-bis-cyclooctatetraeneoxypropane yields two different regio-spin isomer anion radicals in equilibrium (COT-O-C(Me)HCH(2)CH(2)-O-COT(*)(-) = (*)(-)COT-O-C(Me)HCH(2)CH(2)-O-COT) that is shifted far to the right. The presence of the unreduced ring perturbs the spin density on the reduced ring. Addition of more electrons generates the diradical dianion ((*)(-)COT-O-C(Me)HCH(2)CH(2)-O-COT(*)(-)), and the anion radical on the secondary side splits the degeneracy of the psuedo-ortho protons of the anion radical on the primary side.     

Über die Konfiguration des Prolins im Ergotamin

It is well known that in the ergot alkaloids of the peptide type the proline appears in thel-configuration. Different methods of acid hydrolysis may lead to various cleavage products; hydrolysis by HCl yieldsd-proline, on the other hand hydrolytic cleavage by means of strongly acid cation exchange resin preserved the orginall-configuration.

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Teilveröffentlichung der Dissertation vonH. Kolassa, Univ. Wien, 1973.     

A highly emissive Cu2N2 diamond core complex supported by a [PNP]- ligand

A Cu2N2 diamond core structure, {(PNP)CuI}2 (2), supported by a [PNP]- ligand (1) ([PNP]- = bis(2-(diisobutylphosphino)phenyl)amide) has been prepared. 2 is highly emissive at ambient temperature in both the solid and solution states and is characterized by a relatively long-lived excited state (tau > 10 mus) and an unusually high quantum yield (phi > 0.65). These observations are consistent with a low degree of structural reorganization between the ground state of 2 and its excited state *2, and also with a high degree of steric protection of the two copper centers of 2 afforded by the bulky [PNP]- ligand. An estimate for the excited-state reduction potential of *2 (ca. -3.2 V vs Fc+/Fc), and the availability of two well-separated and reversible ground-state redox processes, suggests that bimetallic copper systems of these types may be interesting candidates to consider for photochemically driving multielectron redox transformations.     

Relaxivity and water exchange studies of a cationic macrocyclic gadolinium(III) complex

We conducted relaxometric and water exchange studies of the cationic [Gd((S,S,S,S)-THP)(H2O)]3+ complex (THP 1,4,7,10-tetrakis(2-hydroxy-propyl)-1,4,7,10-tetraazacyclododecane). While the NMRD profiles obtained are typical for DOTA-like complexes (DOTA = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate), variable-temperature 7O NMR investigations revealed a relatively high water exchange rate (k(298)(ex) = 1.89 x 10(7) s(-1)). These results differ from those reported for other cationic tetraamide macrocyclic Gd(III) complexes, which exhibit characteristically low exchange rates. Since the low exchange rates are attributed partially to the geometry of the M isomer (square antiprismatic) in the tetraamide derivatives, the atypical water exchange rate observed in [Gd((S,S,S,S)-THP-(H2O)]3+ may result from a twisted square antiprismatic structure in this complex and from the relatively high steric strain at the water coordination site as a result of the presence of methyl groups at the alpha-position with respect to the Gd(III)-bound O atoms of THP.     

Studies on borate esters 1 : The ph dependence of the stability of esters of boric acid and borate in aqueous medium as studied by 11B NMR

The pH dependent stability of esters of boric acid and borate with glycol, glycolic acid, oxalic acid and glyceric acid as dihydroxy compounds has been studied. ¹¹B NMR provides a suitable analytical tool for the quantitative determination and structure elucidation of the various esters in aqueous medium. The pH dependent stability of esters of boric acid and borate is formulated in a general rule of thumb: esters of boric acid and borate with dihydroxy compounds in aqueous medium show the highest stability at that pH where the sum of the charges of the free esterifying species is equal to the charge of the ester.     

The search for bishomoaromatic semibullvalenes and barbaralanes: computational evidence of their identification by UV/Vis and IR spectroscopy and prediction of the existence of a blue bishomoaromatic semibullvalene

Time-dependent B3LYP/6-31G calculations have been performed at the optimized C(2) or C(2v) geometries of several substituted semibullvalenes (1(deloc)) and barbaralanes (2(deloc)), to compare the computed vertical electronic excitation energies with the temperature-dependent, long-wavelength absorptions that have been observed in the UV/vis spectra of some of these compounds by Quast and co-workers. The excellent agreement between the calculated vertical excitation energies and the observed values of lambda(max) provides strong support for the identification of the bishomoaromatic species 1(deloc) and 2(deloc) as the source of these absorptions. Furthermore, the CN stretching frequencies, computed for the C(2) geometry of 1,5-dimethyl-2,6-dicyano-4,8-diphenylsemibullvalene (1f(deloc)), fit the low-frequency absorptions seen in the IR spectrum of 1f, thus furnishing independent evidence that bishomoaromatic geometries of semibullvalenes have, in fact, been observed spectroscopically. B3LYP/6-31G calculations predict that 2,6-dicyano-4,8-diphenylsemibullvalene 1c has a C(2) equilibrium geometry (1c(deloc)) and that the long-wavelength UV/vis absorption (lambda(max) = 585 nm) and CN stretching frequencies (2192 and 2194 cm(-1)) computed for 1c(deloc) should serve to identify this bishomoaromatic semibullvalene when it is synthesized.     

Direct measurements of (p, \gamma) cross-sections at astrophysical energies using radioactive beams and the Daresbury Recoil Separator

There are a number of astrophysical environments in which the path of nucleosynthesis proceeds through proton-rich nuclei. These nuclei have traditionally not been available as beams, and thus proton-capture reactions on these nuclei could only be studied indirectly. At the Holifield Radioactive Ion Beam Facility (HRIBF), some of the first direct measurements of (p, $ \gamma$ ) cross-sections on radioactive beams have been made. The Daresbury Recoil Separator (DRS) has been used to separate the recoils of interest from the unreacted primary beam and identify them in an isobutane-filled ionization counter. First data from ¹⁷F (p, $ \gamma$ ¹⁸Ne and ⁷Be (p, $ \gamma$ ⁸B measurements are presented.     

Cassie-Baxter to Wenzel state wetting transition: Scaling of the front velocity

We experimentally study the dynamics of water in the Cassie-Baxter state to Wenzel state transition on surfaces decorated with assemblies of micrometer-size square pillars arranged on a square lattice. The transition on the micro-patterned superhydrophobic polymer surfaces is followed with a high-speed camera. Detailed analysis of the movement of the liquid during this transition reveals the wetting front velocity dependence on the geometry and material properties. We show that a decrease in gap size as well as an increase in pillar height and intrinsic material hydrophobicity result in a lower front velocity. Scaling arguments based on balancing surface forces and viscous dissipation allow us to derive a relation with which we can rescale all experimentally measured front velocities, obtained for various pattern geometries and materials, on one single curve.