S3O2--an unusual structure with pi*-pi* interaction

The structures and relative stabilities of 15 S3O2 isomers have been investigated by G3X(MP2), CCSD(T)/aug-cc-pVTZ and MRCI/CASSCF calculations. The global energy minimum is a three-membered sulfur ring with two adjacent sulfoxide groups in a trans conformation, i.e. a vic-disulfoxide of C2 symmetry. The SS bond lengths are 2.136 (2x) and 2.354 angstroms at the CCSD(T)/cc-pVTZ level of theory. There is a strong interaction between the pi* orbitals of the two S=O moieties both in the trans and in the almost degenerate cis conformer. The corresponding chain-like singlet and triplet isomers of connectivity OSSSO lie close in energy (ca. 67 kJ mol(-1)) while five-membered and branched four-membered rings are significantly less stable. The structure of S3O2 is in contrast to that of the isoelectronic analogue S5, which exists as a five-membered twisted heterocycle.     

S4NR (R=Methyl,n-Octyl) as Novel Chelating Ligands in Titanocene Complexes and First Synthesis of Small Sulfurimide Heterocycles SnNR (n=5, 6)

Not the expected insertion into a S−S bond but rather substitution of one NR unit takes place in the reaction of [Cp₂Ti(CO)₂] with cyclic tetrasulfurdiimides 1,4-S₄(NR)₂. The product obtained contains the novel ligand S₄NR and serves as precursor in the synthesis of small SN heterocycles not accessible before (see below).     

Interaction of zinc oxide clusters with molecules related to the sulfur vulcanization of polyolefins ("rubber")

The vulcanization of rubber by sulfur is a large‐scale industrial process that is only poorly understood, especially the role of zinc oxide, which is added as an activator. We used the highly symmetrical cluster Zn₄O₄ (T_d) as a model species to study the thermodynamics of the initial interaction of various vulcanization‐related molecules with ZnO by DFT methods, mostly at the B3LYP/6‐31+G* level. The interaction energy of Lewis bases with Zn₄O₄ increases in the following order: CO62H₄3H₆2S₂<1,4‐C₅H₈2O2S3N?CH₃COO^?. The corresponding binding energies range from ?57 to ?262 kJ mol^?1. However, Brønsted acids react with the Zn₄O₄ cluster with proton transfer from the ligand molecule to one of the oxygen atoms of Zn₄O₄, and these reactions are all strongly exothermic [binding energies [kJ mol^?1] in parentheses: H₂O (?183), MeOH (?171), H₂S (?245), MeSH (?230), C₃H₆ (?121), and CH₃COOH (?255)]. The important vulcanization accelerator mercaptobenzothiazole (C₇H₅NS₂, MBT) containing several donor sites reacts with the Zn₄O₄ cluster with proton transfer from the NH group to one of the oxygen atoms of ZnO, and in addition the exocyclic thiono sulfur atom and the nitrogen atom coordinate to one and the same zinc atom, resulting in a binding energy of ?247 kJ mol^?1. A second isomer of [(MBT)Zn₄O₄] with a strong O? H???N hydrogen bond rather than a Zn? N bond is only slightly less stable (binding energy ?243 kJ mol^?1). The NH form of free MBT is 36 kJ mol^?1 more stable than the tautomeric SH form, while the sulfurized MBT derivative benzothiazolyl hydrodisulfide C₇H₅NS₃ (BtSSH) is most stable with the connectivity >CSSH.     

Vapor Phase Growth of Functional Pentacene Films at Atmospheric Pressure

Compared to traditional vacuum evaporation techniques for small organic molecules, organic vapor phase deposition (OVPD) possesses a extra processing parameter: the pressure of process gas P_ch. Here, the influence of large P_ch variations (from 0.1 mbar to atmospheric pressure) on pentacene thin film growth is explored. OVPD operation at higher P_ch is characterized by lower carrier gas velocities and lower organic diffusivities. These result in an invariance of the material utilization efficiency over the entire pressure span and in an advantageous equilibrium evaporation regime in the source. An increase in P_ch yields rough pentacene layers. Classical nucleation theory is applied to demonstrate how the pressure rise triggers homogeneous nucleation in the gas phase, causing the observed roughening. The use of lower deposition rates, higher dilution flow rates, and higher substrate temperatures result in the suppression of gas phase nucleation and the growth of smooth pentacene films at atmospheric pressure. Using these optimized conditions, state‐of‐the‐art pentacene thin film transistors with saturation mobilities above 0.9 cm²/Vs are reproducibly fabricated. p‐Type circuits are also made and a 19‐stage ring oscillator with a stage delay of 51 μs at a supply voltage of 15 V is demonstrated.     

Charge‐Transfer Complexes Between the Sulfur Molecules SO2, S2O,S3, SONH,and SOCl2 and the Amine Donors NH3 and NMe3 — A theoretical Study

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.     

Isotope shift in molybdenum

The isotope shift in molybdenum has been studied in 16 lines of the arc and 6 lines of the spark spectrum for all stable isotopes by means of a photoelectric recording Fabry-Perot spectrometer with digital data processing. Mass shift and field shift were separated by two independent methods and were compared with the results of Hartree-Fock calculations. In the field shift large crossed-second-order effects ind ⁵ s ⁷ S and⁵ S were observed, which could be explained quantitatively by theory. The changes in mean square nuclear charge radii were evaluated from three 5s-5p transitions between different multiplets. The relativeδ〈r ² 〉 values are: [92, 94] 1; [94, 96] 0.854(3); [96, 98] 0.665(4); [98, 100] 1.003(5); [95, 97] 0.703(5);. [94, 95] 0.270(4); [96, 97] 0.119(5). The absolute values can be obtained withδ〈r ² 〉 ^{92, 94}=0.226(19)fm².     

Photolithographic patterning of organic photodetectors with a non-fluorinated photoresist system

We report on the fabrication of organic photodetectors (OPD) based on isolated islands of P3HT:PCBM. Pattern transfer to the active material was done with photolithography based on non-fluorinated solvents and the excessive organic semiconductor was removed with oxygen plasma reactive ion etching. The photoresist system used was found to be benign to the P3HT:PCBM layer as confirmed by absorption, thickness and roughness measurements. Current–voltage characteristics and external quantum efficiency (EQE) remained unchanged after the patterning process. It was demonstrated that it is possible to photolithographically pattern isolated islands with 200 μm edge length with the same dark current density (<10⁻⁵ A/cm² at −2 V bias voltage) and photocurrent density (>5 × 10⁻³ A/cm² at −2 V). Furthermore, concerning the solar cell performance, the patterned, small-area devices showed power conversion efficiency of 2.1% and fill-factor of 60%. Dark current was observed to depend on the size of the remaining semiconductor island, which was demonstrated on OPDs with diameter of 50 μm. The presented results show the feasibility of fabrication of isolated devices based on organic semiconductors patterned with non-fluorinated photolithography.