Solvent controlled self-assembly at the liquid-solid interface revealed by STM

The effect of solvent on the two-dimensional (2D) supramolecular ordering of monodendron 1 at the liquid-solid interface has been systematically investigated by means of scanning tunneling microscopy (STM). Solvents range from those with hydrophilic solvating properties, such as alkylated alcohols and acids, to hydrophobic solvents such as alkylated aromatics and alkanes. Dramatic differences in the 2D ordering are observed depending on the nature of the solvent. Of particular interest is the fact that in hydrophobic solvating solvents, such as aliphatic and aromatic hydrocarbons, solvent molecules are coadsorbed in the 2D molecular network while this is not the case for alkylated alcohols or acids. Furthermore, in the case of the coadsorbing solvents, a striking influence of the alkyl chain length has been observed on the 2D pattern formed. The solvent and alkyl chain length dependences are discussed in terms of molecule-molecule interactions (homo and hetero) and molecule-substrate interactions.     

Disassembly via an environmentally friendly and efficient fluorous phase constructed with dendritic architectures

Traditionally the fluorous phase is generated with perfluorinated alkyl groups that are usually perfluorooctyl or longer and are bioaccummulative and biopersistent and therefore, are considered environmentally unfriendly. Here we report a new concept for the construction of the fluorous phase. This concept is based on the amplification of the fluorous effect with the help of dendritic architectures containing very short semifluorinated groups on their periphery. This new concept was demonstrated by the convergent synthesis of the first and second generation AB₃ and AB₂ benzyl ether dendrons functionalized on their periphery via catalytic nucleophilic addition of their phenolates to perfluoropropyl vinyl ether. The resulting dendrons are liquids. Their fluorous phase affinity was analyzed and demonstrated that the dendritic architecture amplifies the fluorous phase at a specific generation by the number of functional groups on the dendron periphery, and at different generations by increasing their generation number. Therefore, this concept is very efficient for the design and synthesis of new fluorous materials. In addition, by contrast with dendrons containing perfluoroalkyl groups on their periphery, the current dendrons mediate the disassembly of their parent building blocks but do not mediate the self‐assembly in a supramolecular architecture. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2498–2508, 2010     

Phase transfer catalyzed single electron transfer–degenerative chain transfer mediated living radical polymerization (PTC‐SET–DTLRP) of vinyl chloride catalyzed by sodium dithionite and initiated with iodoform in water at 43 °C

To accelerate the living radical polymerization (LRP) of vinyl chloride (VC) in water the phase transfer catalyzed single electron transfer–degenerative chain transfer mediated living radical polymerization (SET–DTLRP) of VC mediated by sodium dithionite (Na₂S₂O₄) was investigated. The fastest polymerization reaction that still produces thermally stable poly(vinyl chloride) (PVC) takes place at 43 °C with the ratio [PTC]₀/[Na₂S₂O₄]₀ = 0.0075/1. Cetyltrimethylammonium bromide (nC₁₆H₃₃(CH₃)₃N⁺Br^?, CetMe₃NBr) was the phase‐transfer catalyst (PTC) of choice. Under these conditions the first, fast stage of SET–DTLRP of VC was accomplished within 7–8 h when the initial ratio monomer/initiator [VC]₀/[CHI₃]₀ was 800. The number‐average molecular weight (M_n) of the resulting PVC was in good agreement with the theoretical molecular weight (M_th). When the [VC]₀/[CHI₃]₀ ratio was 4800, the fast step of the reaction was accomplished within 17 h, to produce 72% monomer conversion. A deviation of the M_n from the M_th was observed in this case. Possible mechanistic explanations for this deviation as well as for the phase transfer catalyzed SET–DTLRP of VC were suggested. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 779–788, 2005     

A comparative computational study of the homolytic and heterolytic bond dissociation energies involved in the activation step of ATRP and SET‐LRP of vinyl monomers

A quantum‐chemical calculation of the homolytic and heterolytic bond dissociation energies of the model compounds of the monomer and dimer is reported. These model compounds include the dormant chloride, bromide, and iodide species for representative activated and nonactivated monomers containing electron‐withdrawing groups as well as for a nonactivated monomer containing an electron‐donor group. Two examples of sulfonyl and N‐halide initiators are also reported. The homolytic inner‐sphere electron‐transfer bond dissociation is known as atom transfer and is responsible for the activation step in ATRP. The heterolytic outer sphere single electron transfer bond dissociation is responsible for the activation step in single electron transfer mediated living radical polymerization (SET‐LRP). The results of this study demonstrated much lower bond dissociation energies for the outer sphere single electron transfer processes. These results explain the higher rate constant of activation, the higher apparent rate constant of propagation, and the lower polymerization temperature for both activated and nonactivated monomers containing electron‐withdrawing groups in SET‐LRP. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1607–1618, 2007     

Kinetic simulation of single electron transfer–living radical polymerization of methyl acrylate at 25 °C

A mechanistic comparison of the ATRP and SET‐LRP is presented. Subsequently, simulation of kinetic experiments demonstrated that, in the heterolytic outer‐sphere single‐electron transfer process responsible for the SET‐LRP, the activation of the initiator and of the propagating dormant species is faster than of the homolytic inner‐sphere electron‐transfer process responsible for ATRP. In addition, simulation experiments suggested that in both polymerizations the rate of deactivation is similar. In SET‐LRP, the Cu(II)X₂/L deactivator is created by the disproportionation of Cu(I)X/L inactive species, while in ATRP its concentration is mediated by the bimolecular termination. The combination of higher rate of activation with the creation of deactivator via disproportionation provides, via SET‐LRP, an ultrafast synthesis of polymers with very narrow molecular weight distribution at room temperature. SET‐LRP is mediated by a catalytic amount of Cu(0), and under suitable conditions, bimolecular termination is virtually absent. Kinetic and simulation experiments have also demonstrated that the amount of water available in commercial solvents and monomers is sufficient to induce the disproportionation of Cu(I)X/L into Cu(0) and Cu(II)X₂/L and, subsequently, to change the polymerization mechanism from ATRP to SET‐LRP. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1835–1847, 2007.