Dye-sensitized photocatalytic hydrogen production: distinct activity in a glucose derivative of a phenothiazine dye.

A thiophene-based donor-acceptor phenothiazine dye has been functionalized with a peripheral glucose unit (PTZ-GLU) to bust its affinity to water and enhance dye-sensitized photogeneration of hydrogen. Compared to the corresponding alkyl derivative (PTZ-ALK), as well as the common hydrophilic triethylene glycol substitution (PTZ-TEG), the sugar derivative shows a lower contact angle; PTZ-GLU performed twice more efficient than PTZ-TEG in the photogeneration of hydrogen in terms of evolved gas and turnover number.

Pyridoneimines and pyridonemethides: substituent- and solvent-tunable intramolecular charge transfer and geometric isomerism.

We have prepared and fully characterized by means of multinuclear NMR and UV-vis spectroscopy a series of pyridoneimines and pyridonemethides in order to show how it is possible to finely tune pi-electron structure properties by properly exploiting substituent and solvent effects. Substituents with different electron-withdrawing capacities were introduced in pyridoneimines 2-4, pyridonemethides 5 and 6, and pyridine sulfonamido derivatives 7-9. The anisochrony of the carbon position of the azinium ring (geometric isomerism) and the exploitation of previously reported (13)C and (15)N shift/pi-electron density relationships allowed the investigation of the extent of intramolecular charge transfer from the donor group to the acceptor pyridinium moiety. By combining different substitutions with the polarity of the surrounding media, we were able to access a whole range of push-pull electron structures in solution, from fully aromatic-zwitterionic to quinoid-neutral, through many possible intermediate situations along the path. Due to the strict correlation between the pi-electron structure of push-pull derivatives and many photonic properties such as nonlinear optical activity, we believe that the achieved results should be valuable for the development of new efficient, tailor-made, heteroaromatic systems with optimized features as advanced organic materials.

A stereospecific synthesis of oxazolinyloxiranes.

Lithiooxiranes 3a and 3b, generated by deprotonation of oxiranes 2a and 2b with s-BuLi at -100 degrees C in Et(2)O, were found to be chemically very stable. trans-Lithiooxirane 3a was also configurationally stable and reacted stereospecifically with electrophiles to give 4a--k. In contrast, cis-lithiooxirane 3b was found to be configurationally much less stable and reacted with electrophiles affording mixtures of diastereomers 4, 7, and 8. After only a very short reaction time, 3b too reacted with electrophiles highly stereospecifically. Deprotonation--deuteration and deprotonation--alkylation of chiral oxazolinyloxiranes 12a and 12b to give oxiranes 12c and 12d were also examined. Semiempirical and ab initio calculations were carried out in an effort to explain the observed stereochemistry.

A spectroscopic and magnetic study of complexes of bis(2-benzothiazolyl)methanate and bis(2-benzoxazolyl)methanate with Co(II), Ni(II), Cu(II) and Zn(II).

The co-ordination geometry of the complexes M(bbtm)2 and M(bbom)2 (M: Co, Ni, Cu, Zn; bbtm, bis(2-benzothiazolyl)methanate; bbom, bis(2-benzoxazolyl)methanate) are discussed on the basis of their IR, Raman, resonance Raman, electronic and ESR spectra. Compounds of Ni, Co, Zn with both ligands and Cu(bbom)2 resulted to have a distorted tetrahedral geometry. The distortion towards a square planar geometry is more marked for the M(bbtm)2 series than for the M(bbom)2 one. It has been impossible to suggest a co-ordination geometry for Cu(bbtm)2, that probably has a polymeric structure.