1-R-2-[(1E,3E)-4-Aminobuta-1,3-dien-1-yl]-1H-benzimidazoles. Synthesis and some transformations

7-Nitropyridobenzimidazolium salts are cleaved with secondary amines to form 2-[(E,E)-4-aminobuta-1,3-dienyl]-1H-benzimidazoles. The latter react with dimethyl acetylene-dicarboxylate to yield 4a-[(E,Z,E)-6-amino-4,5-dimethoxycarbonylhexa-1,3,5-trien-1-yl]-1,2,3,4-tetra(methoxycarbonyl)-4a,5-dihydropyrido[1,2-a]benzimidazoles.     

Chemoselectivity of [4 + 2] cycloaddition in <Emphasis Type="Italic">N</Emphasis>-maleyl- and <Emphasis Type="Italic">N</Emphasis>-allyl-2,6-difurylpiperidin-4-ones

On the basis of a transition state conformation analysis, an attempt was made to explain the high chemoselectivity of intramolecular [4 + 2] cycloaddition in 3-alkyl-2,6-difuryl-N-maleylpiperidin-4-ones. It was shown that the thermal Diels–Alder reaction in these piperidine derivatives takes place through the “boat” conformation and leads to the formation of hydrogenated 1-alkyl-4-(2-furyl)-2H-8,10a-epoxy-pyrido[2,1-a]isoindol-2-ones. The alternative regioisomers, 3-alkyl-4-(2-furyl)-2H-8,10a-epoxy-pyrido[2,1-a]isoindol-2-ones, are hardly formed at all. At the same time, the intramolecular Diels–Alder reaction in the isostructural 3-alkyl-N-allyl-2,6-difurylpiperidin-4-ones, takes place non-regioselectively from the “chair” conformation.     

Observation of muon pairs in neutrino interactions at Serpukhov 70 GeV accelarator

A search for dimuons produced in a spark chamber experiment in neutrino and antineutrino beams of the Serpukhov accelerator is reported. The clear dimuon signal has been observed in vN interactions. R_v = N(2ω)/N(1ω)? (6.2 ± 1.7) × 10^?3 in the energy interval 7.5 ÷ 30 GeV. From antineutrino data we conclude that in the same energy range $\text{R}{}_{\mathrm{<mtext>v</mtext>}}\text{? 1.1. × 10}{}^{\mathrm{?2}}\text{(90\% C.L.)}$.     

Regioselectivity in the reactions of polyfunctionalised pyrroles with nucleophiles

The polyfunctionalised pyrrole, 3,5-dichloro-1H-pyrrole-2,4-dicarbaldehyde reacts with secondary amines by condensation with the 2-carbaldehyde to give methylene-substituted pyrroles, while its N-alkyl derivatives undergo substitution of the 5-chloro group to give 5-substituted pyrroles.     

Exceptionally fast radiative decay of a dinuclear platinum complex through thermally activated delayed fluorescence

A novel dinuclear platinum(ii) complex featuring a ditopic, bis-tetradentate ligand has been prepared. The ligand offers each metal ion a planar O^N^C^N coordination environment, with the two metal ions bound to the nitrogen atoms of a bridging pyrimidine unit. The complex is brightly luminescent in the red region of the spectrum with a photoluminescence quantum yield of 83% in deoxygenated methylcyclohexane solution at ambient temperature, and shows a remarkably short excited state lifetime of 2.1 μs. These properties are the result of an unusually high radiative rate constant of around 4 × 10⁵ s⁻¹, a value which is comparable to that of the very best performing Ir(iii) complexes. This unusual behaviour is the result of efficient thermally activated reverse intersystem crossing, promoted by a small singlet–triplet energy difference of only 69 ± 3 meV. The complex was incorporated into solution-processed OLEDs achieving EQE_max = 7.4%. We believe this to be the first fully evidenced report of a Pt(ii) complex showing thermally activated delayed fluorescence (TADF) at room temperature, and indeed of a Pt(ii)-based delayed fluorescence emitter to be incorporated into an OLED.

Efficient thermally activated delayed fluorescence (TADF) in a brightly luminescent diplatinum(ii) complex results in significant enhancement of the radiative decay rate.     

Optical methods in studies of structural transformations in thin organic films

The examples of phase transitions in Langmuir-Blodgett films of polyvinylidene fluoride (PVDF) and in the surface layer of polystyrene were chosen to demonstrate the great potential of using luminescent molecular probes for studying the heterogeneity of the surfaces of solids and thin films, as well as structural transformations and phase transitions in systems of different natures. The method provides unique information on the local properties of surfaces and thin films when used in combination with other techniques.     

Exploring the Subtle Effect of Aliphatic Ring Size on Minor Actinide-Extraction Properties and Metal Ion Speciation in Bis-1,2,4-Triazine Ligands

The synthesis and evaluation of three novel bis-1,2,4-triazine ligands containing five-membered aliphatic rings are reported. Compared to the more hydrophobic ligands 1 – 3 containing six-membered aliphatic rings, the distribution ratios for relevant f-block metal ions were approximately one order of magnitude lower in each case. Ligand 10 showed an efficient, selective and rapid separation of Am^III and Cm^III from nitric acid. The speciation of the ligands with trivalent f-block metal ions was probed using NMR titrations and competition experiments, time-resolved laser fluorescence spectroscopy and X-ray crystallography. While the tetradentate ligands 8 and 10 formed Ln^III complexes of the same stoichiometry as their more hydrophobic analogues 2 and 3 , significant differences in speciation were observed between the two classes of ligand, with a lower percentage of the extracted 1:2 complexes being formed for ligands 8 and 10 . The structures of the solid state 1:1 and 1:2 complexes formed by 8 and 10 with Y^III, Lu^III and Pr^III are very similar to those formed by 2 and 3 with Ln^III. Ligand 10 forms Cm^III and Eu^III 1:2 complexes that are thermodynamically less stable than those formed by ligand 3 , suggesting that less hydrophobic ligands form less stable An^III complexes. Thus, it has been shown for the first time how tuning the cyclic aliphatic part of these ligands leads to subtle changes in their metal ion speciation, complex stability and metal extraction affinity.