Studies toward the synthesis of oximidines I and II

The synthesis of compound 1, a precursor for the synthesis of the oximidine II core structure 2, is described. An undesired C8-C9 isomerization occurred during the intramolecular Castro-Stephens reaction leading to macrocyle 3. The thermodynamic driving force for this unexpected isomerization was established by DFT and MP2 calculations. [reaction: see text]     

4,5-Dimethylene -1,2-dioxane and derived Diels-Alder adducts

4,5-Dimethylene-1,2-dioxane (1) was prepared by zinc-induced debromination of 4,5-bis (bromomethyl)-1,2-dioxacylohexa-4-en (4) obtained from 2,3-bis (bromomethyl-1,3-butadiene (3) by reaction with singlet oxygen. Diels-Alder additions of 1 with singlet oxygen, dimethyl acetylenedicarboxylate and N-methyl-1,2,4-triazoline-3,5-dione gave adducts 2,6 and 8 respectively. 3,4-Disubtituted furans 5 and 9 were obtained from peroxides 4 and 8 by cobalt (II) tetraphenylporphyrin catalyzed rearrangement.     

Direct Electrochemical Capture and Release of Carbon Dioxide Using an Industrial Organic Pigment: Quinacridone

Limiting anthropogenic carbon dioxide emissions constitutes a major issue faced by scientists today. Herein we report an efficient way of controlled capture and release of carbon dioxide using nature inspired, cheap, abundant and non‐toxic, industrial pigment namely, quinacridone. An electrochemically reduced electrode consisting of a quinacridone thin film (ca. 100 nm thick)on an ITO support forms a quinacridone carbonate salt. The captured CO₂ can be released by electrochemical oxidation. The amount of captured CO₂ was quantified by FT‐IR. The uptake value for electrochemical release process was 4.61 mmol g^?1. This value is among the highest reported uptake efficiencies for electrochemical CO₂ capture. For comparison, the state‐of‐the‐art aqueous amine industrial capture process has an uptake efficiency of ca. 8 mmol g^?1.     

A tetraphenylethene based polarity dependent turn-on fluorescence strategy for selective and sensitive detection of Hg in aqueous medium and in living cells

A turn-on fluorescent chemosensor strategy based on the change in the polarity of aggregation induced emission active tetraphenylethene is presented for the detection of Hg²⁺ in aqueous medium and in living cells. The sensing mechanism involves the formation of nonpolar fluorescent aggregates of tetraphenylethene molecules by elimination of polar moieties of TPE with Hg²⁺ interaction.     

Controlled Synthesis of Substituted Benzobasketene Derivatives

The addition of benzyne to trans‐7,8‐dibromobicyclo[4.2.0]octa‐2,4‐diene ( 6 ) led to the formation of dibromide 7 . The dehydrobromination of 7 followed by replacement of the Br‐atom with a CN substituent gave 9 . Photolysis of 9 in acetone at 254 nm yielded the desired monosubstituted benzobasketene derivative 10 . Bromination of monobromide 8 followed by dehydrobromination furnished the symmetrically substituted dibromo compound 15 . Further bromination of 7 followed by dehydrobromination resulted in the formation of the dibromides 20 and 21 . Substitution of the Br‐atoms in 15, 20 , and 21 with CN substituents and photolysis of the formed dicarbonitriles 16, 23 , and 24 gave the target benzobasketene‐dicarbonitriles 17, 25 , and 26 , respectively.     

On the capriciousness of the FCCF Karplus curve

Numerous well-behaved Karplus curves correlating dihedral angle (phi) and NMR coupling constants (3JXY) exist for X-C-Z-Y fragments with X or Y = H, C, F, and P. Absent is the enigmatic F-C-C-F moiety. By calculating the four Ramsey contributions to 3JFF for F-CH2-CH2-F, a pleasing phi/3JFF curve with both positive and negative regions arises. Unlike the H-C-C-H curve, F-C-C-F is PSO vs FC dominated. The latter and the F lone electron pairs cause both the negative J values and the substituent-induced J-leveling effect.     

Anthracene‐containing conjugated polymer showing four optical transitions upon doping: A spectroscopic study

An anthracene‐containing poly(arylene‐ethynylene)‐alt‐poly(arylene‐vinylene) (PAE‐PAV) of general constitutional unit (? Ph? C?C? Anthr? C?C? Ph? CH?CH? Anthr? CH?CH)_n bearing two 2‐ethylhexyloxy solubilizing side chains on each phenylene (Ph) unit has been synthesized and characterized. The basic electrochemical characterization was done, showing the existence of two non‐reversible oxidation and one reversible reduction peaks. The optical properties, the real and imaginary part of the dielectric function, were probed using spectroscopic ellipsometry (SE). The vibrational structure of the undoped/doped polymer was investigated using Fourier transformed infrared spectroscopy. A strong change in the polaronic absorption was observed during the doping, which after modeling revealed the existence of two separated transitions. The optical changes upon doping were additionally recorded using the SE technique. Similar to the results from FT‐IR spectroscopy, two new in‐the‐gap absorptions were found. Moreover, the electrical conductivity as well as the mobility of positive carriers were measured. In the undoped state, the conductivity of the polymer was found to be below the detection limit (<μS cm^?1), after doping the conductivity increased to 0.69 S cm^?1. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 338–346     

Characterization of CuTe nanofilms grown by underpotential deposition based on an electrochemical codeposition technique

Journal of Solid State Electrochemistry - This study reports the synthesis of semiconductor CuTe nanofilms using underpotential deposition (UPD) technique based on the simultaneous,...     

Synthesis and Structural Studies of 2,2′-[(2E,5E)-hexane-2,5-diylidenedi-nitrilo]-dibenzenethiol and 2-Hydroxybenzaldehyde (2E,5E)-hexane-2,5-diylidenehydrazone ligands and their Mononuclear Cu(II) and Ni(II) Complexes

Monomeric copper(II) and nickel(II) complexes with tetradentate two new ligands, 2,2′-[(2E,5E)-hexane-2,5-diylidenedi- nitrilo]dibenzenethiol(H₂L) and 2-hydroxybenzaldehyde (2E,5E)-hexane-2,5-diylidenehydrazone(H₂L¹) have been synthesized and characterized by elemental analyses, magnetic moments, molar conductance, ¹H-NMR and ¹³C-NMR, IR, mass spectral studies, theoretical calculations (MM2 and AM1) molecular methods. The mononuclear metal complexes of H₂L and (H₂L¹) were found to have a 1:1 metal:ligand ratio. Elemental analyses, stoichiometric and spectroscopic data of metal complexes indicated that the metal ions were coordinated to the sulphur (-SH) and/or (-OH) oxygen and imine nitrogen atoms (C = N). All of the data obtained from spectral, and molecular mechanics (MM2) or semi empirical calculations (AM1) studies support the structural properties of ligands and its Cu(II) and Ni(II) metal complexes.     

A Soluble Donor–Acceptor Double-Cable Polymer: Polythiophene with Pendant Fullerenes

Summary.  We report the synthesis and the spectroscopic properties of a novel soluble thiophene-based copolymer carrying pendant fullerene moieties (donor–acceptor double-cable polymer). Photoinduced absorption (PIA) experiments on spin cast films reveal a photoinduced electron transfer from the polythiophene chain onto the fullerene moieties. The performance of photovoltaic devices produced with this copolymer is also discussed. Corresponding author. E-mail: antonio.cravino@jku.at Received August 16, 2002; accepted (revised) August 26, 2002