Photophysical behaviour of azaphenanthrenes

Nitrogen position and internal heavy atom effects on the radiative and radiationless transitions from the lowest excited states of the isomeric azaphenanthrenes and some of their methyl, chlorine and bromine derivatives have been studied in E.P.A. solutions at 77 K. The nitrogen position affects the fluorescence and S₁-T₁ intersystem crossing rates more than the phosphorescence and T₁-S₀ intersystem crossing rates. Small differences in the behaviour of 9-azaphenanthrene are enhanced in non-hydroxylic solvents and at room temperature, and it is inferred that (n, π*) states play a more important role in the photophysical behaviour of this isomer. Halogen, substitution in all the isomers increases the phosphorescence rate, induces a smaller increase in the T₁-S₀ intersystem crossing rates and has a negligible effect on the fluorescence rate.     

Lifetime measurements of two-photon excited vibronic levels in the low pressure limit: naphthalene

Single vibronic lifetimes of two-photon excited states are measured in the low pressure limit for naphthalene. The two-photon spectrum, besides yielding new states in S₁, is also free of the interference from the neighborhood of the S₂, known from one-photon experiments, and hence unperturbed lifetimes can be measured to higher excess energies. The overall pattern of lifetimes with excess energy including both one-photon and two-photon states shows that the vibronic structure is subordinate to an overall monotonic decrease, much as found earlier for β-naphthylamine. This indicates, at least for naphthalene, that radiationless processes into triplets are dominated by Franck—Condon factors and not by vibronic inductions and promoting modes.     

Influence of Jahn-Teller coupling on the magnetic properties of transition metal complexes with orbital triplet ground terms: magnetization and electronic Raman studies of the titanium(III) hexa-aqua cation

Magnetization and electronic Raman data are presented for salts of the type Cs[Ga:Ti](SO(4))(2) x 12H(2)O, which enable a very precise definition of the electronic structure of the [Ti(OH(2))(6)](3+) cation. The magnetization data exhibit a spectacular deviation from Brillouin behavior, with the magnetic moment highly dependent on the strength of the applied field at a given ratio of B/T. This arises from unprecedented higher-order contributions to the magnetization, and these measurements afford the determination of the ground-state Zeeman coefficients to third-order. The anomalous magnetic behavior is a manifestation of Jahn-Teller coupling, giving rise to low-lying vibronic states, which mix into the ground state through the magnetic field. Electronic Raman measurements of the 1%-titanium(III)-doped sample identify the first vibronic excitation at approximately 18 cm(-1), which betokens a substantial quenching of spin-orbit coupling by the vibronic interaction. The ground-state Zeeman coefficients are strongly dependent on the concentration of titanium(III) in the crystals, and this can be modeled as a function of one parameter, representing the degree of strain induced by the cooperative Jahn-Teller effect. This study clearly demonstrates the importance that the Jahn-Teller effect can have in governing the magnetic properties of transition metal complexes with orbital triplet ground terms.     

Ligand exchange reactions with η6-arene-η5-cyclopentadienyliron cations under thermal or photochemical conditions

Reactions of various η⁶-arene-η⁵-cyclopentadienyliron or substituted cyclopentadienyliron cations with trimethyl, triethyl or triphenyl phosphite under either thermal or photochemical conditions all resulted in the replacement of the arene ligand with three phosphite ligands to give η⁵-tris(trimethyl, triethyl or triphenyl phosphite)-η⁵-cyclopentadienyliron or substituted cyclopentadienyliron cations. The yields of the phosphite complexes were higher from photolysis than from the analogous thermolysis. Photolysis of the η⁶-chlorobenzene-η⁵-cyclopentadienyliron cation (IX) carried out in the presence of a more basic or more electron-rich aromatic ligand resulted in the exchange of the chlorobenzene of IX with the more basic arene, thus providing synthetic routes to cyclopentadienyliron complexes that may be difficult to prepare by other means. New complexes synthesized in this way are the η⁶-2-phenylethyl tosylate-η⁵-cyclopentadienyliron cation and the CpFe⁺ complexes of thiophene, 2-methylthiophene, 3-methylthiophene and 2,5-dimethylthiophene.     

Hydrophilic polymer membranes containing carboxylic groups—I. Acrylic acid—methyl methacrylate—glycidyl methacrylate copolymers

Copolymers of acrylic acid, methyl methacrylate and glycidyl methacrylate have been synthesized and converted into cross-linked hydrophilic membranes by successive treatments with heat, alkali solution and acidic solution. The copolymerization was carried out in solution using tetrahydrofuran and p-dioxane as solvents. The polymer was obtained as a clear viscous solution at yields of approximately 95%. The polymerization was stopped before gelation took place. This gelation resulted from the reaction of epoxy and carboxylic groups of the polymeric chain. The polymerization time ranged from 3.5 to 7 hr depending on the content of the glycidyl methacrylate in the feed. The monomer mixture consisted of 25–45 mol% of acrylic acid, 40–70 mol% of methyl methacrylate and 2.5–15 mol% of glycīdyl methacrylate. With increasing content of acrylic acid, the membranes became soft and elastic; with decreasing content, they became brittle and hydrophobic. The swelling of the cured polymeric film increased with increase in the acrylic acid content of the monomer mixture and decreased with increasing glycidyl methacrylate content. Dialysis runs were conducted with sodium chloride, urea and a series of ethylene glycols with molecular weights up to 600. The permeability coefficients through the membranes for the ethylene glycols were similar to those through a commercial cellulose membrane (Cuprophane). The permeability proportional to $\text{(permeant molecular wt)}{}^{\mathrm{<mtext>?</mtext><mtext>1</mtext><mtext>2</mtext>}}$. The membranes showed very low permeabilities to sodium chloride compared with those of commercial nonionic membranes. This appears to be due to the ionic exclusion mechanisms expected for ion exchange membranes.     

On the time dependence of the formation of a condensed film in the adsorption of adenosine at the interface mercury/electrolyte

The formation of a condensed film in the adsorption of adenosine at the interface mercury/electrolyte was investigated by means of the differential capacity-time dependence combined with the potential-step method. A mathematical function is given which approximates the experimentally found time dependence of the film formation. This function can theoretically be derived with the assumption that the mechanism of the formation of the condensed film is similar to that of two-dimensional nucleation in the case of metal deposition. A possible molecular mechanism of film formation is discussed.     

Zum Dissoziationsverhalten dimerer Metallhalogenide und zur Bildung von MnAl2Cl8

Dissoziation Behaviour of Dimerie Metal Halides and the Formation of MnAl₂Cl₈ The thermal dissoziation was measured of the gaseous dimeric metal halides Al₂Cl₆, Ga₂Cl₆, In₂Cl₆, and Mn₂I₄ and the formation of the gaseous chloride complex MnAl₂Cl₈ by MnCl_2,f and Al₂Cl_6,g in a membrane manometer. The enthalpy and the entropy of these reactions were derived.     

Dynamics of the accumulation of the alkaloids ofReseda luteola structure of lutine and lutinine

Summary The biosynthesis of the alkaloids ofAmmothamnus lehmannii Bge. have been studied by supplying the plants with [1,5-¹⁴C₂] cadaverine. It has been shown that cadaverine is a precursor of sophocarpidine, sophocarpine, and pachycarpine. Possible routes of interconversions have been studied by supplying the plants with the tritium-labelled alkaloids [³H] sophocarpine, [³H] matrine, and [³H] pachycarpine.V. I. Lenin Tashkent State University. Institute of Plant Biochemistry, Academy of Sciences of the German Democratic Republic, Halle. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 776–780, November–December, 1976.     

Acetylation of lagochilin

The acetylation of lagochilin and its derivatives with acetic anhydride in the presence of pyridine has been studied by PMR spectroscopy. It has been shown that the manifestation of the polyfunctionality of lagochilin in acetylation reactions with acetic anhydride is connected with a change in the nature of the process of solvation of the reaction forms with the subsequent replacement of the hydrogen atoms of the hydroxy groups by acetyl groups.V. I. Lenin Tashkent State University. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 46–49, January–February, 1980.     

Synthesis of naphthyridines and phenanthrolines using catalysts based on transition and rare-earth metals

Liquid-phase condensation of 3-, 4-, and 8-aminoquinolines with aliphatic and aromatic aldehydes catalyzed by transition and rare-earth metal complexes is an efficient method for synthesis of substituted 1,7- and 1,6-naphthyridines and 1,10-phenanthrolines.Institute of Organic Chemistry, Ural Branch, Russian Academy of Sciences, 450054 Ufa; Eastern Scientific-Research Institute of Coal Chemistry, 620219 Sverdlovsk. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1139–1148, May, 1992.