Construction of Annulated Spiro[4.4]-nonane-diones via the Tandem [4 + 2]-Cycloaddition/Aromatization Reaction.

A method for the synthesis of both symmetric and asymmetric fused spiro[4.4]-nonane-dione derivatives has been developed. It is based on a Diels-Alder reaction of spiro[4.4]nona-2,7-diene-1,6-dione as a dienophile component followed by immediate aromatization of the adduct. An active diene component can be generated using the tetrabromoxylene/NaI system, the 1,3-diphenylisobenzofuran/BF3 system, or substituted cyclones.

Fast Recombination of Charge-Transfer State in Organic Photovoltaic Composite of P3HT and Semiconducting Carbon Nanotubes Is the Reason for Its Poor Photovoltaic Performance.

Although the photovoltaic performance of the composite of poly-3-hexylthiophene (P3HT) with semiconducting single-walled carbon nanotubes (s-SWCNT) is promising, the short-circuit current density jSC is much lower than that for typical polymer/fullerene composites. Out-of-phase electron spin echo (ESE) technique with laser excitation of the P3HT/s-SWCNT composite was used to clarify the origin of the poor photogeneration of free charges. The appearance of out-of-phase ESE signal is a solid proof that the charge-transfer state of P3HT+/s-SWCNT- is formed upon photoexcitation and the electron spins of P3HT+ and s-SWCNT- are correlated. No out-of-phase ESE signal was detected in the same experiment with pristine P3HT film. The out-of-phase ESE envelope modulation trace for P3HT/s-SWCNT composite was close to that for the polymer/fullerene photovoltaic composite PCDTBT/PC70BM, which implies a similar distance of initial charge separation in the range 2-4 nm. However, out-of-phase ESE signal decay with delay after laser flash increase for P3HT/s-SWCNT composite was much faster, with a characteristic time of 10 µs at 30 K. This points to the higher geminate recombination rate for the P3HT/s-SWCNT composite, which may be one of the reasons for the relatively poor photovoltaic performance of this system.

Symmetric spirenes: promising building blocks for new generation opto-electronic materials.

Spiroconjugated hydrocarbons, and in particular spirenes, show unique properties among the numerous π-conjugated materials; they are quite rigid systems, with a subsequently small excitation reorganization energy, and hence are excellent hole transporting materials. Furthermore they show chiroptical properties and an efficient intramolecular through-space charge transport capability, leading to thermally-activated delayed fluorescence. In this work an efficient protocol for computing different properties of spirenes is described and validated. This protocol is then employed to investigate the structural properties, intra- and inter-ring interactions, vibrational and optical spectra of a series of symmetric spirenes, whose properties are compared with the corresponding non-spiroconjugated cyclic hydrocarbons. The effect of oxidation and reduction is analysed in detail.

P2O5-Promoted Cyclization of Di[aryl(hetaryl)methyl] Malonic Acids as a Pathway to Fused Spiro[4.4]nonane-1,6-Diones.

Conventional spiro-linked conjugated materials are attractive for organic optoelectronic applications due to the unique combination of their optical and electronic properties. However, spiro-linked conjugated materials with conjugation extension directed along the main axis of the molecule are still only rare examples among the vast number of spiro-linked conjugated materials. Herein, the synthesis, leading to π-extended spiro-linked conjugated materials─spiro[4.4]nonane-1,6-diones and spiro[5.5]undecane-1,7-diones─has been developed and optimized. The proposed design concept starts from readily available malonic esters and contains several steps: double alkylation of malonic ester with bromomethylaryl(hetaryl)s; conversion of a malonic ester into the corresponding malonic acid; electrophilic spirocyclization of the latter into the annulated spiro[4.4]nonane-1,6-dione or spiro[5.5]undecane-1,7-dione in the presence of phosphorus pentoxide. On the basis of these insights, the developed method yielded spiro-linked conjugated cores fused with benzene, thiophene, and naphthalene, decorated with active halogen atoms. The structures of the synthesized spirocycles were determined by single-crystal X-ray diffraction analysis. Benzene fused spiro[4.4]nonane-1,6-dione decorated with bromine atoms was transformed into V-shape phenylene-thiophene co-oligomer type spirodimers via Stille coupling. The spiro-bis(4-n-dodecylphenyl)-2,2'-bithiophene derivative possessed high photoluminescence properties in both solution and solid state with a photoluminescence quantum yield (PL QY) of 38%.

Boron-containing nucleosides as tools for boron-neutron capture therapy.

Despite the significant progress in cancer cure, the development of new approaches to cancer therapy is still of great importance since many deadly tumors remain untreatable. Boron neutron capture therapy (BNCT), proposed more than eighty years ago, is still considered a potentially advantageous approach. Irradiation of cells containing 10B isotopes with epithermal neutrons and the consequent decay of boron nuclei releases particles that deposit high energy along a very short path, inflicting heavy damage on the target cells but sparing the neighbouring tissue. Delivery and preferential accumulation of boron in cancer cells are the major obstacles that slow down the clinical use of BNCT. Since DNA damage caused by irradiation is the major reason for cell death, the incorporation of boron-containing nucleotides into the DNA of cancer cells may significantly increase the efficacy of BNCT. In this review, we discuss the current state of knowledge in the synthesis of boron-containing nucleosides and their application for BNCT with a special focus on their possible incorporation into genomic DNA.

A Weakly Antiferromagnetically Coupled Biradical Combining Verdazyl with Nitronylnitroxide Units.

An antiferromagnetically (AFM) coupled biradical based on oxoverdazyl and nitronylnitroxide was synthesized in 46 % yield using Sonogashira coupling. The obtained heterobiradical evidenced distinct properties of both radical entities in solution. Depending on the solvent, the prepared biradical crystallized in two different forms. SQUID magnetization measurements on Form II showed coupling constants JintraII /kB =-2.1 K and zJinterII /kB =-11.5 K. Consequently, total intermolecular exchange interactions are five times larger than the intramolecular ones. Further, DFT calculations explained this phenomenon and indicated the advantage of Form I for further in-depth investigations.

Crystal packing control of a trifluoromethyl-substituted furan/phenylene co-oligomer.

Furan/phenylene co-oligomer single crystals are considered as future materials for organic optoelectronics. Here, the effects of trifluoromethyl substituents on the crystallization, structure and optical properties of furan/phenylene co-oligomer 1,4-bis{5-[4-(trifluoromethyl)phenyl]furan-2-yl}benzene are studied systematically. The solution growth methods and physical vapor transport result in the formation of three polymorphs depending on the growth method and the solvent. Single-crystal X-ray analysis reveals the crystal structures to correspond to H-, J- or mixed aggregates. All obtained crystals exhibit high photoluminescence efficiency and have optical properties which strongly depend on the crystal packing. Variable-temperature X-ray powder diffraction analysis shows the thermal transition of two forms (H- and J-aggregates) into a third one (mixed aggregate). Terminal trifluoromethyl groups induce weak intermolecular interactions which control the crystal packing and optical properties of co-oligomer single crystals.

A quantitative topological descriptor for linear co-oligomer fusion.

A purely topological descriptor for the quantitative classification of fully or partially fused linear quasi-one dimensional centre-symmetric molecules is proposed. The index also makes it possible to quantitatively correlate optoelectronic properties with the molecular topology without involving an explicit calculation of the molecular electronic structure.

The Suzuki-Miyaura reaction as a tool for modification of phenoxyl-nitroxyl radicals of the 4H-imidazole N-oxide series.

2-(3,5-Di-tert-butyl-4-hydroxyphenyl)-5-(4-iodophenyl)-4,4-dimethyl-4H-imidazole 3-oxide reacts with phenylboronic acid and its substituted derivatives in a cross-coupling reaction of the Suzuki-Miyaura type to form 5-biphenyl derivatives of 4H-imidazole-N-oxide. Interaction of the same compound with B2(pin)2 in the presence of PdCl2(PPh3)2 proceeds through the formation of intermediate 1,3,2-dioxoborolane and leads to the product of homocoupling: biphenyl-bis(imidazole). Oxidation of the resultant imidazoles with lead dioxide quantitatively yields stable conjugated phenoxyl-nitroxyl mono- and diradicals, which are of interest as electroactive paramagnetic materials. The crystal structure of the monoradical, 2,6-di-tert-butyl-4-[1-oxido-4-(biphenyl-4-yl)-5,5-dimethyl-1H-imidazole-2(5H)-ylidene]cyclohex-2,5-dienone, its magnetic susceptibility, EPR spectra of the obtained hybrid radicals in solution, and cyclic voltammetry characteristics of 4H-imidazoles were studied.