CONTROLLING THE 3D NANOSCALE ORGANIZATION OF BULK HETEROJUNCTION POLYMER SOLAR CELLS

In this study,the three dimensional nanoscale organization in the photoactive layers of poly(3-hexylthiophene) (P3HT) and a methanofullerene derivative (PCBM) is revealed by transmission electron tomography.After annealing treatment,either at elevated temperature or during slow solvent evaporation,nanoscale interpenetrating networks are formed with high crystalline order and favorable concentration gradients of both components through the thickness of the photoactive layer.Such a tailored morphology acco...     

Synthesis of 4-hydroxy-6,9-difluorobenz[g]isoquinoline-5,10-diones and conversions to 4-hydroxy-6,9-bis[(aminoalkyl)amino]-benz[g]isoquinoline-5,10-diones

Synthetic procedures have been developed which lead to 4-hydroxy-6,9-difluorobenz[g]isoquinoline-5,10-dione ( 4a ) and its 3-methyl analogue 4b . Attempts to displace the fluorides from 4a with N,N-dimethylethylenediamine were unsuccessful. Analogue 4a on treatment with N-(t-butoxycarbonyl)ethylene diamine led to 15 , formed from addition of the nucleophilic amine to C-3. On the other hand, analogue 4b , on treatment with N,N-dimethylethylenediamine led to the anticipated difluoride displacement product 3c . The protection of the hydroxy group of 4a by benzylation with phenyldiazomethane led to 4c which on treatment with N-(t-butoxycarbonyl)ethylene diamine or N,N-dimethylethylenediamine led to the corresponding 6,9-bis-substituted analogues 18a and 18b , respectively. Reductive debenzylations of 18a and 18b by hydrogenation over Pearlman's catalyst also effected partial reductions of the quinone. However, air oxidation of the over reduced products led to 3a and 3b , respectively. Treatment of 3a with hydrogen chloride gas led to the hydrochloride salt of 3d . Addition of O-p-Methoxybenzyl-N,N'-diisopropylurea to 4a led to the p-methoxybenzyl analogue 4d . Treatment of 4d with N,N-dimethylethylene diamine or N-(t-butoxycarbonyl)ethylene diamine led to displacements of the fluorides to yield 18c and 18d , respectively. Deprotection of 18c to 3b was accomplished using methanesulfonic acid. Treatment of 18d with trifluoroacetic acid followed by addition of maleic acid led to dimaleate salt of 3d .     

Characterization of the motion of spin probes and spin labels in amorphous polymers with two-dimensional field-step ELDOR

The motion of nitroxide spin probes and spin labels in amorphous polymers is studied below the glass transition temperature with a two-dimensional pulsed electron double-resonance experiment. Polystyrene and a liquid crystalline side group polymer are studied using both spin probes and spin labels covalently bound to specific sites along the polymer chain. Two methyl acrylic polymers differing only in their side group structure and polyvinylacetate are compared and large differences in the molecular dynamics deduced from both the nuclear and the electron spin relaxation rates are observed as the glass transition is approached. The results demonstrate the complexity of small amplitude motion in simple polymers below the glass transition temperature and show that it is very sensitive to the packing in the polymer. © 1996 John Wiley & Sons, Inc.     

Electronic Structure of the Aqueous Vanadyl Ion Probed by 9 and 94 GHz EPR and Pulsed ENDOR Spectroscopies and Density Functional Theory Calculations

The aqueous vanadyl ion ([VO(H(2)O)(5)](2+)) has been investigated by X-band EPR, 94 GHz W-band EPR, and ESE-ENDOR. These experiments reveal information about the hyperfine (|A(xx)| = 208.5 MHz, |A(yy)| = 208.5 MHz, |A(zz)| = 547.0 MHz), and nuclear quadrupole coupling (|e(2)qQ| = 5.6 MHz) of the (51)V nucleus. The measured nuclear quadrupole coupling parameters are compared to values determined by density functional theory calculations (|e(2)qQ| = 5.2 MHz). These theoretical calculations illustrate that axial ligands and molecular distortions can alter the magnitude of the nuclear quadrupole interaction.     

1,1-Addition von Zinn- und Bleiverbindungen an Isonitrile Umsetzungen von Isonitrilen mit Halogeniden der IV. und V. Gruppe, 1. Mitt.

Zusammenfassung Isonitrile reagieren mit Zinntetrahalogeniden unter Einschiebung in Zinn-Halogen-Bindungen zu Halogencarbimino-zinnhalogeniden. Bei Umsetzungen mit organosubstituierten Zinnhalogeniden reagieren bevorzugt die Zinn-Halogen-Bindungen; nur Phenylisonitril wurde (unter forcierten Bedingungen) auch in Zinn-Kohlenstoff-Bindungen eingeschoben. In manchen Fällen entstehen dimere oder polymere Produkte. Triphenylbleibromid reagiert mit Phenylisonitril zur entsprechenden Tetracarbiminobleiverbindung.

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1,1-additions of tin and lead compounds to isonitriles

The reaction of isonitriles with tin(IV) halides yields halogenocarbiminotinhalides by insertion into tin-halogen bonds. In organosubstituted tin halides the tin-halogen bonds are more reactive towards insertion of isonitriles than the tin-carbon bonds. Under forced conditions however, phenylisonitrilisonitril also inserts into Sn–C bonds. A tetracarbimino-lead compound was obtained by reacting phenylisonitrile with triphenyllead bromide.

     

Massenspektrometrische Untersuchungen von PhthalocyaninenPc—MeX n

PhthalocyaninesPc?Me(III)X andPc?Me(V)X ₃ were obtained by reacting anhydrous metal halides with phthalodinitrile and di-lithium-phthalocyanine, resp. A phthalocyanine containing niobium(V) was prepared for the first time. Mass spectrometric investigation of the products formed show the molecular ion in the case of chloro-aluminum-, chloro-indium- and tribromo-niobium-phthalocyanine. The mass spectra of chloro-scandium-, chloro-yttrium- and tribromo-tantalum-phthalocyanine showed neither peaks of the molecular mass nor metal containing fragments of the phthalocyanine structure. Mass spectrometric results seem to depend critically on the purity of the compounds employed.     

The bruker high-frequency-EPR system

The design and performance of the first commercial 94 GHz continuous-wave (CW-)/Fourier transform (FT-) EPR and ENDOR spectrometer are described. The spectrometer design is based on a heterodyne microwave bridge using an X-band intermediate frequency (IF), a hybrid magnet system, a variable-temperature, top-loading TeraFlex probehead with a TE₀₁₁ cavity as well as the ELEXSYS-line digital electronics and the Xepr software package. The W-band bridge can be driven by a CW- or pulse-IF unit and delivers a microwave power of 5 mW at 94 GHz. In pulse mode the power is sufficient for a π/2 pulse of 100 ns at a resonatorQ-value of 3000. The magnet system consists of a 6 T split-coil superconducting magnet and a water-cooled room-temperature coil. The main coil can be swept over the full range from 0 to 6 T. The room-temperature coil has a 800 G sweep range around the persistent field of the main magnet. The ENDOR probe features a tuned circuit for¹H nuclei allowing an RF π-pulse of 8 μs with a 200 W amplifier. A broad-band setup is used for other nuclei. The E680 FT-EPR system utilizes the PatternJet pulse programmer and the SpecJet high-speed transient signal averager. The concerted action of these two devices results in a pulse EPR sensitivity equal or higher than in CW-EPR. Selected examples indicating the performance of the 94 GHz CW/FT-EPR and ENDOR systems are shown.     

Mono-(BOC)-Protected Diamines. Synthesis of tert-Butyl-N-alkyl-N-(2-aminoethyl)carbamates and tert-Butyl-N-[2-(alkylamino)ethyl] Carbamates

We wish to report preparative pathways to the mono-(BOC)-protected diamines 1a-d and 2a-c.     

Umsetzungen von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekülen, 2. Mitt.: Reaktionsprodukte von Aminobenzonitrilen mit Halogenboranen

Both 4-aminobenzonitrile and 3-aminobenzonitrile react with halogenoboranes to yield mainly the corresponding amine-halogenoboranes and further products derived from the latter by elimination of hydrogen halide. In contrast, reaction between halogenoboranes and 2-aminobenzonitrile leads to insertion of the nitrile group into one of the B-halogen bonds. Derivatives of the 1.3.2-diazaboranaphthalene ring result from reactions of the insertion products with the amino group with or without elimination of hydrogen halides.     

The synthesis of 6,9-bis[(aminoalkyl)amino] substituted benzo[g]quinoxaline-, benzo[g]quinazoline- and benzo-[g]phthalazine-5,10-diones via regiospecific displacements

The synthesis of 6,9-difluoro substituted benzo[g]quinoxaline-5,10-diones ( 3A ), benzo[g]quinazoline-5,10-diones ( 3B ) and benzo[g]phthalazine-5,10-diones ( 3C ) have been accomplished. Treatment of 3A, 3B or 3C with diamines or N-(t-butoxycarbonyl)ethylenediamine led to the corresponding 6,9-bis[(aminoalkyl)amino]-substituted analogues related to 2A, 2B and 2C , respectively. The mono-substituted derivatives 4h and 4i could be isolated from displacements commencing from 3A . A competitive ring-opening of the pyrimidine ring of 2C occurred during the reaction with N,N-dimethylethylenediamine. Removal of the BOC-protecting group from 2Ac led to the hydrochloride salt 2Ab . A novel synthetic pathway to 6,9-dihydroxybenzo[g]-phthalazine-5,10-dione ( 21a ) was developed. Conversion of 21a to the ditosylate 21b was readily accomplished. Treatment of 21b with N,N-dimethylethylenediamine or N-(t-butoxycarbonyl)ethylenediamine led to 2Ca and 2Cc , respectively. Removal of the BOC-protecting group from 2Cc with trifluoroacetic acid followed by ion-exchange led to the hydrochloride salt 2Cb . Treatment of ditosylate 21b with N-(t-butoxycar-bonyl)ethylenediamine also led to the mono-substituted analogue 25a along with a small amount of the O-S cleavage product 25b . Treatment of 25a with N,N-dimethylethylenediamine led to the unsymmetrically substituted derivative 25c which was converted into the trifluoroacetate salt 25d.