The effect of ligand on the rate of propagation of Cu(0)‐wire catalyzed SET‐LRP of MA in DMSO at 25 °C

The effect of initial ligand concentration on the apparent rate constant of propagation of single‐electron transfer living radical polymerization (SET‐LRP) of MA in DMSO at 25 °C was examined using various lengths of Cu(0) wire as catalyst. It was determined that unlike other parameters such as initiator concentration, solvent concentration, and deactivator concentration, no simple external rate‐order for the ligand concentration could be determined. Rather, the response of the rate of SET‐LRP to initial ligand concentration is complex and is likely determined by a competition of ligand‐dependent extent of disproportionation as well as the role of ligand concentration in the surface mediated activation process. Results suggest that a minimum concentration of ligand is needed to achieve both acceptable reaction rate and reaction control, and therefore, ligand concentration must be considered in designing experimental conditions for SET‐LRP. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5629–5638, 2009     

Synthesis of α,ω‐di(iodo)PVC and of four‐arm star PVC with identical active chain ends by SET‐DTLRP of VC initiated with bifunctional and tetrafunctional initiators

Na₂S₂O₄‐catalyzed single‐electron transfer – degenerative chain transfer‐mediated living radical polymerization (SET‐DTLRP) of VC initiated with the bifunctional initiators 1,2‐bis(iodopropionyloxy)ethane, dimethyl 2,5‐diiodohexanedioate, and bis(2‐methoxyethyl)‐2,5‐diiodohexanedioate as well as the tetrafunctional initiator pentaerythritol tetrakis(2‐iodopropionate) is reported. This SET‐DTLRP was performed in water at ambient temperature in the presence of polyvinyl alcohol and hydroxypropyl methylcellulose surfactants and provides methods for the synthesis of α,ω‐di(iodo)PVC with two identical active chain ends and of four‐arm star PVC with four identical active chain ends. These difunctional and tetrafunctional derivatives of PVC are also macroinitiators for the synthesis of ABA triblock copolymers and four‐arm star block copolymers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 635–652, 2009     

Mimicking “nascent” Cu(0) mediated SET‐LRP of methyl acrylate in DMSO leads to complete conversion in several minutes

Cu(0) was prepared via disproportionation of Cu(I)Br in the presence of Me₆‐TREN in various solvents in a glove box. The resulting nanopowders were used as mimics of “nascent” Cu(0) catalyst in the single‐electron transfer living radical polymerization (SET‐LRP) of methyl acrylate (MA), providing faster polymerization than any commercial Cu(0) powder, Cu(0) wire, or Cu(I)Br and achieving 80% conversion in only 5 min reaction time. Despite the high rate, a living polymerization was observed with linear evolution of molecular weight, narrow polydispersity, no induction period, and high retention of chain‐end functionality. In addition to providing an unprecedentedly fast, yet controlled LRP of MA, these studies suggest that the very small “nascent” Cu(0) species formed via disproportionation in SET‐LRP are the most active catalysts. Thus, when bulk Cu(0) powder or wire may be the most abundant catalyst and dictates the overall kinetics, any Cu(0) produced via disproportionation will be rapidly consumed and contributes to the overall catalytic cycle. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 403–409, 2010     

New efficient reaction media for SET‐LRP produced from binary mixtures of organic solvents and H2O

SET‐LRP is mediated by a combination of solvent and ligand that promotes disproportionation of Cu(I)X into Cu(0) and Cu(II)X₂. Therefore, the diversity of solvents suitable for SET‐LRP is limited. SET‐LRP of MA in a library of solvents with different equilibrium constants for disproportionation of Cu(I)X such as DMSO, DMF, DMAC, EC, PC, EtOH, MeOH, methoxyethanol, NMP, acetone and in their binary mixtures with H₂O was examined. H₂O exhibits the highest equilibrium constant for disproportionation of Cu(I)X. The apparent rate constant of the polymerization exhibits a linear increase with the addition of H₂O. This is consistent with higher equilibrium constants for disproportionation generated by addition of H₂O to organic solvents. Furthermore, with the exception of alcohols and carbonates, the rate constant of polymerization in binary mixtures could be correlated with the Dimroth‐Reichardt solvent polarity parameter. This is consistent with the single‐electron transfer mechanism proposed for SET‐LRP that involves a polar transition state. These experiments demonstrate that the use of binary mixtures of solvents with H₂O provides a new, simple and efficient method for the elaboration of a large diversity of reaction media that are suitable for SET‐LRP even when one of the two solvents does not mediate disproportionation of Cu(I)X. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5577–5590, 2009     

Transfer, amplification, and inversion of helical chirality mediated by concerted interactions of C3-supramolecular dendrimers

The synthesis, structural, and retrostructural analysis of two libraries containing 16 first and second generation C(3)-symmetric self-assembling dendrimers based on dendrons connected at their apex via trisesters and trisamides of 1,3,5-benzenetricarboxylic acid is reported. A combination of X-ray diffraction and CD/UV analysis methods demonstrated that their C(3)-symmetry modulates different degrees of packing on the periphery of supramolecular structures that are responsible for the formation of chiral helical supramolecular columns and spheres self-organizable in a diversity of three-dimensional (3D) columnar, tetragonal, and cubic lattices. Two of these periodic arrays, a 3D columnar hexagonal superlattice and a 3D columnar simple orthorhombic chiral lattice with P222(1) symmetry, are unprecedented for supramolecular dendrimers. A thermal-reversible inversion of chirality was discovered in helical supramolecular columns. This inversion is induced, on heating, by the change in symmetry from a 3D columnar simple orthorhombic chiral lattice to a 3D columnar hexagonal array and, on cooling, by the change in symmetry from a 2D hexagonal to a 2D centered rectangular lattice, both exhibiting intracolumnar order. A first-order transition from coupled columns with long helical pitch, to weakly or uncorrelated columns with short helical pitch that generates a molecular rotator, was also discovered. The torsion angles of the molecular rotator are proportional to the change in temperature, and this effect is amplified in the case of the C(3)-symmetric trisamide supramolecular dendrimers forming H-bonds along their column. The structural changes reported here can be used to design complex functions based on helical supramolecular dendrimers with different degree of packing on their periphery.     

Synthesis,structural analysis,and self-assembly of phenylene ethynylene oligomers and their ?F, ?CF3, and ?CH3 substituted derivatives

Oligomers consisting of aromatic building blocks separated by alkynyl units were synthesized by Sonogashira cross-coupling of aryl halides with terminal acetylenes. Strong electron acceptors such as  F and  CF₃ and weak electron donors like  CH₃ were placed as substituents on one of the benzene rings. Acetyl-protected sulfhydryl groups were attached to one end of these molecules to promote their self-organization on gold surfaces. The electron-transport properties of such self-assembled monolayers (SAMs) are highly sensitive to the local order of the molecules in the solid state. Single crystals were analyzed by X-ray diffraction experiments that revealed structural details that could lead to a better understanding of the electron-transport properties. The unsymmetrical substitution of the aromatic rings by electron-active groups in the ortho-, meta-, or para positions resulted in changes of such molecular parameters as bonding and torsion angles and planarity. These parameters, in turn, can affect the angle of the molecular attachment to a gold substrate and the density of the resulting SAMs. Patterned SAMs of some of these molecules and comparison alkane thiols were obtained on gold by microcontact printing or flooding. The SAM thickness was determined by spectroscopic ellipsometry. Surface potential differences between adjacent SAMs or between SAMs and the gold substrate were measured by scanning surface potential microscopy under ambient conditions. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 541–550, 2004     

Living radical polymerization of vinyl chloride initiated with iodoform and catalyzed by nascent Cu0/tris(2‐aminoethyl)amine or polyethyleneimine in water at 25 °C proceeds by a new competing pathways mechanism

The first example of living radical polymerization of vinyl chloride carried out in water at 25 °C is reported. This polymerization was initiated by iodoform and catalyzed by nascent Cu⁰ produced by the disproportionation of Cu^I in the presence of strongly Cu^II binding ligands such as tris(2‐aminoethyl)amine or polyethyleneimine. The resulting poly(vinyl chloride) was free of structural defects, had controlled molecular weight and narrow molecular weight distribution, contained two ～CHClI active chain ends, and had a higher syndiotacticity (62%) than the one obtained by conventional free‐radical polymerization at the same temperature (56%). This novel polymerization proceeds, most probably, by a combination of competitive pathways that involves activation by single electron transfer mediated by nascent Cu⁰ and degenerative chain transfer. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3283–3299, 2003     

Accelerated iterative strategy for the divergent synthesis of dendritic macromolecules using a combination of living radical polymerization and an irreversible terminator multifunctional initiator

Our laboratory has reported the elaboration of an iterative strategy for the synthesis of dendritic macromolecules from conventional monomers. This synthetic method involves a combination of self‐regulated metal‐catalyzed living radical polymerization initiated from arenesulfonyl chlorides and an irreversible terminator multifunctional initiator (TERMINI). The previous TERMINI, (1,1‐dimethylethyl)[[1‐[3,5‐bis(S‐phenyl‐4‐N,N′ diethylthiocarbamate)phenyl]ethenyl]oxy]dimethylsilane, was prepared in nine reaction steps. The replacement of the previous TERMINI with one that requires only three steps for its synthesis, diethylthiocarbamic acid S‐{3‐[1‐(tert‐butyl‐dimethyl‐silanyloxy)‐vinyl]‐5‐diethylcarbamoylsulfanyl‐phenyl} ester, and the use of the more reactive Cu₂S/2,2′‐bipyridine rather than the Cu₂O/2,2′‐bipyridine self‐regulated catalyst have generated an accelerated method for the synthesis of dendritic macromolecules. This method provides rational design strategies for the synthesis of dendritic macromolecules with different compaction by the use of a single monomer. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4894–4906, 2005