Influence of added salts on the cage escape yields in the photoredox quenching of Ru(bpy)2+3 excited states

The influence of electrolytes on the photoredox kinetics and cage escape yields of redox products (π_redox) in the quenching of Ru(bpy)^2+*₃ by methylviologen (MV²⁺), Tl^III and Hg^II have been investigated. For all three quenchers π_redox appears to be strongly dependent on the nature of the anion. Photoelectrochemical cells based on the latter systems are described.     

Visible Light Induced Water Cleavage in CdS Dispersions Loaded with Pt and RuO2, Hole Scavenging by RuO2

Illumination of aqueous CdS dispersions loaded with Pt and RuO₂ by visible light produces hydrogen and oxygen in stoichiometric proportion. No degradation of the photocatalyst is noted after 60 h of irradiation time. The RuO₂ deposit on the particle surface greatly accelerates the transfer of holes from the semiconductor valence band to the aqueous solution thus inhibiting photocorrosion.     

Structures of Addition Products of Acetylenedicarboxylic Acid Esters with Various Dinucleophiles. An application of C,H-spin-coupling constants

Heterocyclic compounds obtained by addition of acetylenedicarboxylic acid esters to thioureas, cyclic amidines and o-difunctionalized aromatic systems have been studied by ¹³C-NMR. In particular, C, H-spin-coupling constants over two and three bonds were used to differentiate between the various constitutional isomers and to establish the configuration of trisubstituted exocyclic C, C-double bonds. The configurational significance and diagnostic value of vicinal cis and trans C,H-spin coupling is again demonstrated in the present series.     

Studies on the Stereochemistry of 2-(Nitromethylidene)-Heterocycles

The ¹H-NMR spectra of 2-(nitromethylidene)pyrrolidine ( 7 ), 1-methyl-2-(nitromethylidene)imidazolidind ( 10 ) and 3-(nitromethylidene)tetrahydrothiazine ( 11 ) in CDCl₃ and (CD₃)₂SO indicate that these compounds have the intramolecularly H-bonded structures (Z)- 7 , (E)- 10 and (Z)- 11 while the N-methyl derivative 8 of 7 is (E)-configurated in both solvents. 1-Benzylamino-1-(methyltio)-2-nitroehtylene ( 13 ), an acylic model, has the H-bonded configuration (E)- 13 in CDCl₃ and in (CD₃)₂SO. 2-(Nitromethylidene)thiazolidine ( 3 ) has the (E)-configuration in CDCl₃ but exists in (CD₃)₂SO as a mixture of (Z)- and (E)-isomers with the former predominating. Both species are detected to varying proportions in a mixture of the two solvents. ¹⁵N-NMR spectroscopy of 3 ruled out unambiguously the nitronic acid structure 6 and the nitromethyleimine structure 5 . The N-methyl derivative 4 of 3 is (Z)-configurated in (CD₃)₂SO. Comparison of the olefinic proton shifts of (Z)- 3 and (Z)- 4 with those of analogues and also of 1,1-bis(methylti)-2-nitroethylene ( 12 ) shows decreased conjugation of the lone pair of electrons of the ring N-atom in (Z)- 3 and (Z)- 4 . This is also supported by ¹³C-NMR studies. Plausible explanations for the phenomenon are offered by postulating that the ring N-atoms are pyramidal in (Z)- 3 and (Z)- 4 and planar in other cases or, alternatively, that the conjugated nitroenamine system gets twisted due to steric interaction between the NO₂-group and the ring S-atom. Single-crystal X-ray studies of 3 and 8 show that the former exists in the (Z)-configuration and the latter in (E)-configuration; the ring N-atom in the former has slightly more pyramidal character than in the latter.     

Redox‐Switchable Ring‐Closing Metathesis: Catalyst Design,Synthesis, and Study

High yielding syntheses of 1‐(ferrocenylmethyl)‐3‐mesitylimidazolium iodide ( 1 ) and 1‐(ferrocenylmethyl)‐3‐mesitylimidazol‐2‐ylidene ( 2 ) were developed. Complexation of 2 to [{Ir(cod)Cl}₂] (cod=cis,cis‐1,5‐cyclooctadiene) or [Ru(PCy₃)Cl₂(?CH‐o‐O‐iPrC₆H₄)] (Cy=cyclohexyl) afforded 3 ([Ir( 2 )(cod)Cl]) and 5 ([Ru( 2 )Cl₂(?CH‐o‐O‐iPrC₆H₄)]), respectively. Complex 4 ([Ir( 2 )(CO)₂Cl]) was obtained by bubbling carbon monoxide through a solution of 3 in CH₂Cl₂. Spectroelectrochemical IR analysis of 4 revealed that the oxidation of the ferrocene moiety in 2 significantly reduced the electron‐donating ability of the N‐heterocyclic carbene ligand (ΔTEP=9 cm^?1; TEP=Tolman electronic parameter). The oxidation of 5 with [Fe(η⁵‐C₅H₄COMe)Cp][BF₄] as well as the subsequent reduction of the corresponding product [ 5 ][BF₄] with decamethylferrocene (Fc*) each proceeded in greater than 95 % yield. Mössbauer, UV/Vis and EPR spectroscopy analysis confirmed that [ 5 ][BF₄] contained a ferrocenium species, indicating that the iron center was selectively oxidized over the ruthenium center. Complexes 5 and [ 5 ][BF₄] were found to catalyze the ring‐closing metathesis (RCM) of diethyl diallylmalonate with observed pseudo‐first‐order rate constants (k_obs) of 3.1×10^?4 and 1.2×10^?5 s^?1, respectively. By adding suitable oxidants or reductants over the course of a RCM reaction, complex 5 was switched between different states of catalytic activity. A second‐generation N‐heterocyclic carbene that featured a 1′,2′,3′,4′,5′‐ pentamethylferrocenyl moiety ( 10 ) was also prepared and metal complexes containing this ligand were found to undergo iron‐centered oxidations at lower potentials than analogous complexes supported by 2 (0.30–0.36 V vs. 0.56–0.62 V, respectively). Redox switching experiments using [Ru( 10 )Cl₂(?CH‐o‐O‐iPrC₆H₄)] revealed that greater than 94 % of the initial catalytic activity was restored after an oxidation–reduction cycle.     

Stretching and collapse of neutral polymer layers under association with ionic surfactants

We provide experimental evidence for stretching and collapse of neutral polymer layers, already adsorbed at an oil-in-water interface, due to its interaction with surfactants. Upon stretching, the first interaction length (2L(0)) follows a power law dependence on surfactant concentration ( proportional, variant C(x)(s), where x approximately 0.5 for cationic surfactants) and collapses in the presence of salt, as a relatively weak power law (C(-y)(s), where y=0.17), in good agreement with brush length decay for polyelectrolyte brushes.     

Base catalyzed rearrangement of some bicyclic ketol acetates.

The ketol $\text{3a}$ and its acetate $\text{3b}$ when refluxed in methanolic potassium hydroxide (5%) were found to rearrange to 4-methyl-8-acetyl-5,6,7,8-tetrahydro-1-naphthol $\text{4}$. The epimeric acetate $\text{3c}$ also behaved likewise. A mechanism is suggested for the rearrangement.