Proton coupled electron transfer reaction of phenols with excited state ruthenium(II) – polypyridyl complexes

The reaction of phenols with the excited state, *[Ru(bpy)₃]²⁺ (E₀ = 0.76 V) and *[Ru(H₂dcbpy)₃]²⁺, (dcbpy = 4,4′‐dicarboxy‐2,2′‐bipyridine) (E₀ = 1.55 V vs. SCE) complexes in CH₃CN has been studied by luminescence quenching technique and the quenching is dynamic. The formation of phenoxyl radical as a transient is confirmed by its characteristic absorption at 400 nm. The k_q value is highly sensitive to the change of pH of the medium and ΔG⁰ of the reaction. Based on the treatment of k_q data in terms of energetics of the reaction and pH of the medium, proton coupled electron transfer (PCET) mechanism has been proposed for the reaction. Copyright © 2010 John Wiley & Sons, Ltd.     

Triplet photochemistry within zeolites through heavy atom effect, sensitization and light atom effect

Methods to generate triplets of organic molecules within zeolites have been established by employing the Zimmerman rearrangement of barrelenes, oxa-di-π-methane rearrangement of β,γ-unsaturated ketones and photodimerization of acenaphthylene as probe reactions. The two methods, heavy cation effect and triplet sensitization, are well established solution techniques and these work well within zeolites. The Zimmerman rearrangement of dibenzobarrelene is enhanced even within Li⁺ and Na⁺ exchanged zeolites and these are believed to be the result of slowing of the rearrangement to dibenzocyclooctatetraene from S₁ through cation-π interaction. The methods described here provide an opportunity to explore the control afforded by the zeolite environment on triplet reactions.     

Comparison of Templating Abilities of Urea and Thioruea During Photodimerization of Bipyridylethyelene and Stilbazole Crystals

Photodimerization of cocrystals of four bispyridylethylenes and two stilbazoles with urea as a template in the solid state has been investigated following our success with thiourea. Four investigated olefins photodimerized quantitatively to a single dimer in the crystalline state only. The reactivity of urea–olefin crystals is understood on the basis of their packing arrangements in the crystalline state. In reactive crystals the adjacent reactive molecules are within 4.2 Å and parallel, whereas the unreactive ones have their adjacent molecules are farther than 4.6Å and nonparallel. Thus, with the knowledge of crystal packing the reactivity of urea–olefin crystals is predictable on the basis of Schmidt's topochemical postulates. The templating property of urea, similar to thiourea, derives from its ability to form hydrogen bonds with itself and the guest olefins. Despite the similarities in molecular structures of urea and thiourea their subtle electronic properties, yet to be fully understood, affect the crystal packing and consequently their reactivity in the crystalline state. Further work is needed to fully exploit the templating properties of urea.     

Photoinduced electron transfer (PET) based Zn2+ fluorescent probe: transformation of turn-on sensors into ratiometric ones with dual emission in acetonitrile

Ratiometric sensors for the detection of metal ions have gained increasing attention due to its self-calibration tendency for the environmental effects. In this context, we have synthesized and characterized a dual emitting ratiometric Zn(2+) probe (1) having acridinedione as a fluorophore and N,N-bis(2-pyridylmethyl)amine (BPA) as a receptor unit. Existence of two different conformation of the molecule with photoinduced electron transfer (PET) from amine moiety to the acridinedione fluorophore leads to dual emission, namely locally excited (425 nm) and anomalous charge transfer emission (560 nm) in aprotic solvents. In the presence of one equivalent of Zn(2+), a 15-fold fluorescence enhancement in the locally excited state together with the quenching of charge transfer emission is observed. The intensity changes at the two emission peaks allow a ratiometric detection of Zn(2+) under PET signaling mechanism. The utilization of PET process for the ratiometric fluorescence change will further signify the importance of PET mechanism in sensing action. Addition of Zn(2+) to 1 in acetonitrile/water mixtures shows a single emission peak with fluorescence enhancement.     

Interfacial regions governing internal cavities of dendrimers. Studies of poly(alkyl aryl ether) dendrimers constituted with linkers of varying alkyl chain length

This report deals with a study of the properties of internal cavities of dendritic macromolecules that are capable of encapsulating and mediating photoreactions of guest molecules. The internal cavity structures of dendrimers are determined by the interfacial regions between the aqueous exterior and hydrocarbon like interior constituted by the linkers that connect symmetrically sited branch points constituting the dendrimer and head groups that cap the dendrimers. Phloroglucinol-based poly(alkyl aryl ether) dendrimers constituted with a homologous series of alkyl linkers were undertaken for the current study. Twelve dendrimers within first, second, and third generations, having ethyl, n-propyl, n-butyl, and n-pentyl groups as the linkers and hydroxyl groups at peripheries in each generation, were synthesized. Encapsulation of pyrene and coumarins by aqueous basic solutions of dendrimers were monitored by UV-vis and fluorescence spectroscopies, which showed that a lower generation dendrimer with an optimal alkyl linker presented better encapsulation abilities than a higher generation dendrimer. Norrish type I photoreaction of dibenzyl ketone was carried out within the above series of dendrimers to probe their abilities to hold guests and reactive intermediate radical pairs within themselves. The extent of cage effect from the series of third generation dendrimers was observed to be higher with dendrimers having an n-pentyl group as the linker.     

Highly selective, sensitive and quantitative detection of Hg2+ in aqueous medium under broad pH range

Amidothiourea linked acridinedione derivatives selectively detect Hg(2+) in unbuffered aqueous solution under broad pH range with both single- and two-photon excitation. The observed linear fluorescence intensity change allows the quantitative detection of Hg(2+) in the concentration range of 22 nM-0.33 μM with the lower detection limit of 2 nM.     

Nonequilibrium interface equations: An application to thermocapillary motion in binary systems

Interface equations are derived for both binary diffusive and binary fluid systems subjected to nonequilibrium conditions, starting from coarse-grained (mesoscopic) models. The equations are used to describe thermocapillary motion of a droplet in both purely diffusive and fluid cases, and the results are compared with numerical simulations. A mesoscopic chemical potential shift owing to the temperature gradient, and associated mesoscopic corrections involved in droplet motion, are elucidated.     

Nonnegativity of principal minors of generalized inverses of P0-matrices

We derive a necessary and sufficient condition under which a reflexive generalized inverse of a singular P₀-matrix is again a P₀-matrix. Simpler conditions are obtained when the rank of the matrix is n?1, where n is the order of the matrix. We then consider the application of these results to singular M-matrices of order n and rank n?1. In particular, for this case we prove that the Moore-Penrose inverse is a P₀-matrix.     

7-Cis isomers of retinal via 7-cis- and 7,9-dicis-β-C18-tetraene ketones : New geometric isomers of vitamin A and carotenoids—I

Based catalyzed condensation of 7-cis- or 7,9-dicis-β-ionylideneacetaldehyde with acetone gave either 7-cis or 7,9-dicis-β-C₁₈-tetraene ketone. Reaction of the tetraene ketone mixture with diethyl cyanomethylphosphonate gave a mixture of 4 isomers of retinonitrile, all believed to have the 7-cis geometry. Partial redution of the retinonitrile mixture with di-isobutylaluminum hydride gave a mixture of retinal isomers. Repeated column chromatography resulted in partial separation of the retinal isomers. Based on NMR data the geometry of the isomers prepared are believed to be 7-cis, 7,13-dicis, and 7,9,13-tricis.     

Synthesis and properties of adenylate trimers A2′p5′A2′p5′A,A2′p5′A3′p5′A and A3′p5′A2′p5′A

Triadenylates with (2′-5′)(2′-5′) and mixed (2′-5′)(3′-5′) and (3′-5′)(2′-5′) linkages respectively were synthesized via the phosphotriester approach followed by deblocking of the fully protected intermediates. The isomeric trimers were characterized by NMR- and CD-spectra and show very similar hypochromicity effects.