Lithiumphthalocyanine: Synthese,Eigenschaften und Kristallstruktur von Bis(triphenylphosphin)iminiumphthalocyaninatolithaten mit verschiedenen Konformationen des Kations

Lithiumphthalocyanines: Synthesis, Properties, and Crystal Structure of Bis(triphenylphosphine)iminiumphthalocyaninatolithates with Different Conformations of the Cation Reaction of tri(n-dodecyl)n-butylammoniumphthalocyaninatolithate, (TDBA)[LiPc^2?] with bis(triphenylphosphin)iminiumbromide, (PNP)Br in dichloromethane yields (PNP)[LiPc^2?]. It crystallizes in the triclinic space group P1 as dichloromethane solvate ( 1 ) and in the monoclinic space group P2₁/n as hydrate ( 2 ). The crystal structures of ( 1 ) and ( 2 ) are reported. Each salt contains two crystallographically slightly different discrete [LiPc^2?]^? anions, in which the square-planar coordinated Li⁺ cation is centered within the planar Pc^2? ligand (D_av.(Li? N_iso) = 1.945 Å). There are three different conformations for the (PNP) cation: ( 1 ) only contains the bent conformer (d_av.(P? N) = 1.575 Å; φ(P? N? P) = 140.8°), while in ( 2 ) an hybrid (d_av.(P? N) = 1.562 Å; φ(P? N? P) = 158.1°) and the linear conformer (d_av.(P? N) = 1.547 Å; φ(P? N? P) = 176.8°) are present. The very soluble, blue-green salts melt at 265°C without decomposition. In accordance with cyclovoltammetric data thin films of (PNP)[LiPc^2?] are oxidized by NO₂ or Br₂ to yield brown violet [LiPc^?]. The electronic absorption spectra and the vibrational spectra are discussed.     

Preparation and evaluation of polar stabilized phase open tubular (SPOT) columns

Summary A method is described for the routine preparation of high resolution stabilized phase open tubular (SPOT) columns. A finely dispersed siliceous material (Cab-O-Sil) is treated with benzyltriphenylphosphoniumchloride and dynamically coated onto the inside wall of glass capillary columns. Additional dynamics coating with a polar stationary phase yields thermostable columns of high efficiency. The columns show favourable adsorption properties and good long term stability. The mechanical stability of the stationary phase film is explained in terms of the rheological behaviour of concentrated disperisons. The designation PLOT columns appers inapplicable, and these columns will be referred to as SPOT columns. A theoretical model, describing band spreading in SPOT columns, is proposed and compared with the experimental results. Some applications in routine use and in ultra trace analysis are presented.     

Sterilization of Polymer Foils with Dielectric Barrier Discharges at Atmospheric Pressure

The emission of UV light as well as chemical reaction in plasmas allow them to be used for decontamination of food packaging. Sterilization efficiency of different dielectric barrier discharge (DBD) setups at atmospheric pressure was investigated for spores of B. subtilis and A. niger sprayed onto PET foils. In normal DBDs the efficiency of spore reduction in different gases (nitrogen, argon, synthetic air) can be related to the UV spectra of these gases in the discharge. With special so-called cascaded dielectric barrier discharges (CDBDs) a fast reduction of viable cells by more than four orders of magnitude is possible within few seconds, even for UV resistant cells. The sealing properties of commonly used PE-PET-laminate can be maintained in CDBD which is not observed for single-gap DBD.     

Macropolyhedral boron-containing cluster chemistry. Cluster assembly about a molybdenum centre. Formation of the 19-vertex [(CO)2MoB16H15C2Ph2]- anion

Fusion of nine-vertex [1-Ph-nido-1-CB8H11] with [Mo(CH3CN)3(CO)3] in the presence of tetramethylnaphthalenediamine gives the nineteen-vertex macropolyhedral metallaborane anion [(CO)2MoB16H15C2Ph2]- with a molybdenum(VI) twelve-atom coordination sphere.     

Monocarbaborane anion chemistry. [COOH], [CH2OH] and [CHO] units as functional groups on ten-vertex monocarbaborane anionic compounds

B(10)H(14) reacts with para-C(6)H(4)(CHO)(COOH) in aqueous KOH solution to give the [nido-6-CB(9)H(11)-6-(C(6)H(4)-para-COOH)](-) anion 1, which undergoes cage closure with iodine in alkaline solution to give the [closo-2-CB(9)H(9)-2-(C(6)H(4)-para-COOH)](-) anion 2. Upon heating, anion 2 rearranges to form the [closo-1-CB(9)H(9)-1-(C(6)H(4)-para-COOH)](-) anion 3. Similarly, B(10)H(14) with glyoxylic acid OHCCOOH in aqueous KOH gives the [arachno-6-CB(9)H(13)-6-(COOH)](-) anion 4, which undergoes cage closure with iodine in alkaline solution to give the [closo-2-CB(9)H(9)-2-(COOH)](-) anion 5. Upon heating, anion 5 rearranges to give the [closo-1-CB(9)H(9)-1-(COOH)](-) anion 6. Reduction of the [COOH] anions 3 and 6 with diisobutylaluminium hydride gives the [CH(2)OH] hydroxy anions [closo-1-CB(9)H(9)-1-(C(6)H(4)-para-CH(2)OH)](-) and [closo-1-CB(9)H(9)-1-(CH(2)OH)](-) 8 respectively. The [closo-1-CB(9)H(9)-1-(C(6)H(4)-para-CH(2)OH)](-) anion 7 can also be made via isomerisation of the [closo-2-CB(9)H(9)-2-(C(6)H(4)-para-CH(2)OH)](-) anion 9, in turn obtained from the [nido-6-CB(9)H(11)-6-(C(6)H(4)-para-CH(2)OH)](-) anion 10, which is obtained from the reaction of B(10)H(14) with terephthaldicarboxaldehyde, C(6)H(4)-para-(CHO)(2), in aqueous KOH solution. Oxidation of the hydroxy anions 7 and 8 with pyridinium dichromate gives the aldehydic [closo-1-CB(9)H(9)-1-(C(6)H(4)-para-CHO)](-) anion 11 and the aldehydic [closo-1-CB(9)H(9)-1-(CHO)](-) anion 12 respectively, characterised as their 2,4-dinitrophenylhydrazone derivatives, the [closo-1-CB(9)H(9)-1-C(6)H(4)-para-CH=N-NHC(6)H(3)(NO(2))(2)](-) anion 13 and the [closo-1-CB(9)H(9)-1-CH=N-NHC(6)H(3)(NO(2))(2)](-) anion respectively.     

A practical synthesis of isomerically pure 1,10-difunctionalized derivatives of the [closo-1-CB9H10] anion

The isomer-free [closo-1-CB9H(8)-1-COOH-10-I]- anion was prepared in four steps and 10% overall yield from B10H14. The key step is the skeletal isomerization of the [closo-2-CB9H8-2-COOH-7-I]- anion to a mixture of the 10- and 6-iodo derivatives of [closo-1-CB9H(9)-1-COOH]- formed in up to a 3:1 ratio. The carboxylic acid 4 was converted to the amine [closo-1-CB9H(8)-1-NH(2)-10-I]- using the Curtius reaction. The relative thermodynamic stability of each product was calculated at the DFT and MP2 levels of theory. The regioselectivity of electrophilic substitution in [closo-CB9H10]- derivatives was briefly investigated using the NBO population analysis of the MP2 wave function.     

Comparison of Laser Chemical Processing and LaserMicroJet for structuring and cutting silicon substrates

This paper deals with the development of a new cutting method for thin silicon solar wafers with liquid-jet-guided lasers (LaserMicroJet®, LMJ, and Laser Chemical Processing, LCP). Several laser systems with different wavelengths were tested to find the optimum laser system and processing parameters in terms of efficient material removal and deep laser cutting. Water and potassium hydroxide were used as carrier liquids to enhance laser ablation. The ablation efficiency was defined as a target parameter and experimentally determined by performing single laser grooves. It is demonstrated that the ablation process of LMJ is mainly affected by silicon melting and then removing by the liquid-jet momentum for single laser grooves. Best result for deep laser grooves is achieved if evaporation dominates the ablation process. Better surface quality referred to laser-induced crystalline damage is presented for a cut wafer with LMJ in comparison to a standard multiwire slurry saw. This shows a great potential of wafering with liquid-jet-guided lasers although no optimal liquid media was used.