Vinyl Polymerization. 418. Polymerization of Vinyl Monomer Initiated by Betaine-Type Polymers in Aqueous Solution

Abstract

Three kinds of betaine-type polymers, which are macromolecular amphoteric electrolytes, were found to be able to polymerize vinyl monomers in aqueous solution through a radical mechanism without any further initiator. Betain-type polymers form hydrophobic areas (HA) in water. Vinyl polymerization commenced in the HA. The effect of the pH of the aqueous solution on polymerization was investigated.     

Vinyl Polymerization. 431. Vinyl Polymerizations Initiated by Block and Random Poly(Styrene-co-Sodium Methacrylate)

Abstract

The polymerization of some kinds of vinyl monomer was found to occur without an ordinary initiator in aqueous solutions of AB-type block or random copolymers of sodium methacrylate with styrene as a so-called “uncatalyzed polymerization.” Although the spin trapping technique showed that the initiation mechanism by the block copolymer was the same as that by the random copolymer, the initiating ability of the block copolymer was lower than that of the random copolymer. Such results are attributable to the difference in the incorporating ability of monomer into the micelles formed by the block copolymer and into the hydrophobic areas formed by the random copolymer.     

Vinyl Polymerization. 436. Effect of Magnetic Field on Uncatalyzed Polymerization

The radical polymerization of vinyl monomers initiated with several kinds of hydrophilic macromolecule was carried out in a magnetic field. The magnetic field promoted the polymerization; the conversion of monomers and the molecular weight of the polymers obtained increased with increasing field strength in the range of 0–0.1 T. The dependence of the composition and tacticity of the mother polymer on the magnitude of the magnetic field was studied. Using graft or block copolymers, which consisted of hard and soft segments, the effect of a magnetic field was further investigated. The degree of hardness and tightness of the hydrophobic areas (reaction areas) formed by the mother polymer in the aqueous solution was found to affect the magnetic field effect on the uncatalyzed polymerization. The overall activation energy obtained in the magnetic field was almost equal to that obtained without a magnetic field.     

Electrical Network of Single‐Crystalline Metal Oxide Nanoclusters Wired by π‐Molecules

In a mixed‐valence polyoxometalate, electrons are usually delocalized within the cluster anion because of low level of inter‐cluster interaction. Herein, we report the structure and electrical properties of a single crystal in which mixed‐valence polyoxometalates were electrically wired by cationic π‐molecules of tetrathiafulvalene substituted with pyridinium. Electron‐transport characteristics are suggested to represent electron hopping through strong interactions between cluster and cationic π‐molecules.     

Mechanism of Back Electron Transfer in an Intermolecular Photoinduced Electron Transfer Reaction: Solvent as a Charge Mediator

Back electron transfer (BET) is one of the important processes that govern the decay of generated ion pairs in intermolecular photoinduced electron transfer reactions. Unfortunately, a detailed mechanism of BET reactions remains largely unknown in spite of their importance for the development of molecular photovoltaic structures. Here, we examine the BET reaction of pyrene (Py) and 1,4‐dicyanobenzene (DCB) in acetonitrile (ACN) by using time‐resolved near‐ and mid‐IR spectroscopy. The Py dimer radical cation (Py₂^.+) and DCB radical anion (DCB^.?) generated after photoexcitation of Py show asynchronous decay kinetics. To account for this observation, we propose a reaction mechanism that involves electron transfer from DCB^.? to the solvent and charge recombination between the resulting ACN dimer anion and Py₂^.+. The unique role of ACN as a charge mediator revealed herein could have implications for strategies that retard charge recombination in dye‐sensitized solar cells.     

Stereospecific and asymmetric polymerization of 1-phenyldibenzosuberyl methacrylate with radical and anionic initiators

Stereospecific and asymmetric (helix-sense-selective) polymerization of 1-phenyldibenzosuberyl methacrylate (PDBSMA) was performed with radical and anionic initiators. A highly isotactic polymer having triad isotacticity greater than 97% was obtained by radical polymerization with (i-PrOCOO)₂ at 40°C. The radical polymerization of PDBSMA in (+)- and (-)-menthol gave (-)-and (+)-polymers, respectively, whose optical activity is ascribed to the prevailing one-handed helical conformation of a polymer chain. The radical copolymerization of PDBSMA with a small amount of an optically active monomer, (+)-phenyl-2-pyridyl-o-tolylmethyl methacrylate, afforded an optically active copolymer with the prevailing one-handed helical structure of PDBSMA sequences. Asymmetric anionic polymerization of PDBSMA was carried out with the complex of N, N′-diphenylethylenediamine monolithium amide and a chiral ligand, (+)-1-(2-pyrrolidinylmethyl)pyrrolidine in toluene at −78°C. The obtained polymer was highly isotactic and optically active due to nearly 100% one-handed helical structure.     

Stabilization of High‐Valence Ruthenium with Silicotungstate Ligands: Preparation,Structural Characterization,and Redox Studies of Ruthenium(III)‐Substituted α‐Keggin‐Type Silicotungstates with Pyridine Ligands, [SiW11O39RuIII(Py)]5−

Ruthenium(III)‐substituted α‐Keggin‐type silicotungstates with pyridine‐based ligands, [SiW₁₁O₃₉Ru^III(Py)]^5?, (Py: pyridine ( 1 ), 4‐pyridine‐carboxylic acid ( 2 ), 4,4′‐bipyridine ( 3 ), 4‐pyridine‐acetamide ( 4 ), and 4‐pyridine‐methanol ( 5 )) were prepared by reacting [SiW₁₁O₃₉Ru^III(H₂O)]^5? with the pyridine derivatives in water at 80 °C and then isolated as their hydrated cesium salts. These compounds were characterized using cyclic voltammetry (CV), UV/Vis, IR, and ¹H NMR spectroscopy, elemental analysis, titration, and X‐ray absorption near‐edge structure (XANES) analysis (Ru K‐edge and L₃‐edge). Single‐crystal X‐ray analysis of compounds 2 , 3 , and 4 revealed that Ru^III was incorporated in the α‐Keggin framework and was coordinated by pyridine derivatives through a Ru? N bond. In the solid state, compounds 2 and 3 formed a dimer through π? π interaction of the pyridine moieties, whereas they existed as monomers in solution. CV indicated that the incorporated Ru^III–Py was reversibly oxidized into the Ru^IV–Py derivative and reduced into the Ru^II–Py derivative.     

The Microwave Spectrum of Methyl Formate (HCOOCH3) in the Frequency Range from 7 to 200 GHz

The rotational spectrum of methyl formate (HCOOCH₃) has been observed in the frequency range from 7 to 200 GHz. We newly assigned 1612 lines in the ground torsional state and simultaneously analyzed both A- and E-species data including previously reported lines on the basis of the internal axis method. A total of 3077 lines were fitted to a 1σ standard deviation of 139 kHz, and molecular parameters were determined.     

Reactions of C60 with Pyridazine and Phthalazine

Cage-opened bisfulleroids are one of suitable building blocks for making a large hole on fullerenes. This work focuses on the Diels-Alder reaction of C₆₀ with azines, among synthetic methods developed thus far, to provide bisfulleroids. Surprisingly, the computational study predicted that the reaction proceeds with normal electron demand in contrast to hitherto considered inverse-electron-demand pathway. The benzoannulation to the pyridazine ring, i. e., phthalazine, resulted in the remarkably shortened reaction time due to the better interaction between the HOMO of phthalazine and the LUMO of C₆₀ as well as stronger 2,3-diaza-1,3-butadiene character in the phthalazine as confirmed crystallographically. Contrary to expectations, the benzobisfulleroid was converted into corresponding orifice-enlarged derivative via the photooxygenation slightly faster than the fulleroid derived from pyridazine.