Can CH⋅⋅⋅π Interactions Be Used To Design Single‐Chain Magnets?

This theoretical study suggests that CH???π stacking interactions between monomeric units can be used to design novel single‐chain magnets (SCMs), as the sign of coupling is predictable and such chains inherently yield negative axial anisotropy, a condition often difficult to achieve in conventional SCMs.     

[Cu32(H)20{S2P(OiPr)2}12]: The Largest Number of Hydrides Recorded in a Molecular Nanocluster by Neutron Diffraction

An air‐ and moisture‐stable nanoscale polyhydrido copper cluster [Cu₃₂(H)₂₀{S₂P(OiPr)₂}₁₂] ( 1_H ) was synthesized and structurally characterized. The molecular structure of 1_H exhibits a hexacapped pseudo‐rhombohedral core of 14 Cu atoms sandwiched between two nestlike triangular cupola fragments of (2×9) Cu atoms in an elongated triangular gyrobicupola polyhedron. The discrete Cu₃₂ cluster is stabilized by 12 dithiophosphate ligands and a record number of 20 hydride ligands, which were found by high‐resolution neutron diffraction to exhibit tri‐, tetra‐, and pentacoordinated hydrides in capping and interstitial modes. This result was further supported by a density functional theory investigation on the simplified model [Cu₃₂(H)₂₀(S₂PH₂)₁₂].     

Pyrrolo‐dC Metal‐Mediated Base Pairs in the Reverse Watson–Crick Double Helix: Enhanced Stability of Parallel DNA and Impact of 6‐Pyridinyl Residues on Fluorescence and Silver‐Ion Binding

Reverse Watson–Crick DNA with parallel‐strand orientation (ps DNA) has been constructed. Pyrrolo‐dC (PyrdC) nucleosides with phenyl and pyridinyl residues linked to the 6 position of the pyrrolo[2,3‐d]pyrimidine base have been incorporated in 12‐ and 25‐mer oligonucleotide duplexes and utilized as silver‐ion binding sites. Thermal‐stability studies on the parallel DNA strands demonstrated extremely strong silver‐ion binding and strongly enhanced duplex stability. Stoichiometric UV and fluorescence titration experiments verified that a single ^2pyPyrdC–^2pyPyrdC pair captures two silver ions in ps DNA. A structure for the PyrdC silver‐ion base pair that aligns 7‐deazapurine bases head‐to‐tail instead of head‐to‐head, as suggested for canonical DNA, is proposed. The silver DNA double helix represents the first example of a ps DNA structure built up of bidentate and tridentate reverse Watson–Crick base pairs stabilized by a dinuclear silver‐mediated PyrdC pair.     

Biofunctionalization of Polyoxometalates with DNA Primers,Their Use in the Polymerase Chain Reaction (PCR) and Electrochemical Detection of PCR Products

The bioconjugation of polyoxometalates (POMs), which are inorganic metal oxido clusters, to DNA strands to obtain functional labeled DNA primers and their potential use in electrochemical detection have been investigated. Activated monooxoacylated polyoxotungstates [SiW₁₁O₃₉{Sn(CH₂)₂CO}]^8? and [P₂W₁₇O₆₁{Sn(CH₂)₂CO}]^6? have been used to link to a 5′‐NH₂ terminated 21‐mer DNA forward primer through amide coupling. The functionalized primer was characterized by using a battery of techniques, including electrophoresis, mass spectrometry, as well as IR and Raman spectroscopy. The functionality of the POM‐labeled primers was demonstrated through hybridization with a surface‐immobilized probe. Finally, the labeled primers were successfully used in the polymerase chain reaction (PCR) and the PCR products were characterized by using electrophoresis.     

Highly Ordered Structure Formation in RAFT‐Synthesized PtBOS‐b‐P4VP Diblock Copolymers

Linear poly(4‐tert‐butoxystyrene)‐b‐poly(4‐vinylpyridine) (PtBOS‐b‐P4VP) diblock copolymers are synthesized using reversible addition–fragmentation chain transfer polymerization. The self‐assembly of four different PtBOS‐b‐P4VP diblock copolymers is studied using small‐angle X‐ray scattering and transmission electron microscopy and a number of interesting observations are made. A tBOS₆₂‐b‐4VP₂₈ diblock copolymer with a weight fraction P4VP of 0.21 shows a disordered morphology of P4VP spheres with liquid‐like short‐range order despite an estimated value of of the order of 50. Increasing the length of the 4VP block to tBOS₆₂‐b‐4VP₁₉₉ results in a diblock copolymer with a weight fraction P4VP of 0.66. It forms a remarkably well‐ordered lamellar structure. Likewise, a tBOS₁₄₆‐b‐4VP₁₂₀ diblock copolymer with a weight fraction P4VP of 0.33 forms an extremely well‐ordered hexagonal structure of P4VP cylinders. Increasing the P4VP block of this block copolymer to tBOS₁₄₆‐b‐4VP₁₉₀ with a weight fraction P4VP of 0.44 results in a bicontinuous gyroid morphology despite the estimated strong segregation of . These results are discussed in terms of the architectural dissimilarity of the two monomers, characterized by the presence of the large side group of PtBOS, and the previously reported value of the interaction parameter, , for this polymer pair.

     

Precision Chain‐Walking Polymerization of trans‐4‐Octene Catalyzed by α‐Diimine Nickel(II) Catalysts Bearing ortho‐sec‐Phenethyl Groups

α‐Diimine nickel complexes bearing bulky ortho‐sec‐phenethyl groups (bis{[N,N′‐(4‐methyl‐2,6‐di‐sec‐phenethylphenyl)imino]‐1,2‐dimethylethane}dibromonickel ( 1 ), bis{[N,N′‐(4,6‐dimethyl‐2‐sec‐phenethylphenyl)imino]‐1,2‐dimethylethane}dibromonickel ( 2 ), bis{[N,N′‐(4‐methyl‐2‐sec‐phenethylphenyl)imino]‐1,2‐dimethylethane}dibromonickel ( 3 )) and {bis[N,N′‐(2,4,6‐trimethylphenyl)imino]‐1,2‐dimethylethane}dibromidonickel ( 4 ) are used as a precatalyst for the polymerization of trans‐4‐octene upon activation with modified methylaluminoxane. These catalysts conduct chain‐walking polymerization of trans‐4‐octene to give polymers possessing propyl and butyl branches with high molecular weight and narrow molecular weight distribution. The branching structure depends on the nickel complex as well as the polymerization temperature, and the ratio of propyl branch was increased with increasing the bulkiness of the ligand and decreasing the polymerization temperature. Consequently, the most bulky 1 among the complexes used is found to polymerize trans‐4‐octene with high 1,5‐regioselectivity at −20 °C to give poly(1‐propylpentan‐1,5‐diyl).

     

Shaping the Light: The Key Factors Affecting the Photophysical Properties of Fluorescent Polymer Nanostructures

To manipulate the functions of nanomaterials more precisely for diverse applications, the controllability and critical influencing factors of their properties must be thoroughly investigated. In this work, the macroscopic and microscopic effects are studied on the photophysical properties of various pyrene‐ended poly(styrene‐block‐methyl methacrylate) nanostructures. Fluorescent polymer nanospheres, nanorods, and nanotubes are prepared by different template‐based methods using anodic aluminum oxide membranes. Chain arrangements and conformations are determined as the key factors affecting the photophysical properties of the fluorescent polymer nanostructures. This work not only gives a deeper understanding of the effects on the photophysical properties of polymer nanomaterials influenced by morphologies, chain arrangements, and chain conformations, but also provides a reference for designing proper fluorescent nanostructures for specific applications.

     

Catalytic chain transfer polymerization of isobutylene: The role of nucleophilic impurities

Fast polymerization of isobutylene (IB) initiated by tert‐butyl chloride using ethylaluminum dichloride·bis(2‐chloroethyl) ether complex (T. Rajasekhar, J. Emert, R. Faust, Polym. Chem. 2017, 8, 2852) was drastically slowed down in the presence of impurities, such as propionic acid, acetone, methanol, and acetonitrile. The effect of impurities on the polymerization rate was neutralized by using two different approaches. First, addition of a small amount of iron trichloride (FeCl₃) scavenged the impurity and formed an insoluble · impurity complex in hexanes. The polymerization rate and exo‐olefin content were virtually identical to that obtained in the absence of impurities. Heterogeneous phase scavenger (FeCl₃) exhibited better performance than homogenous phase scavengers. In the second approach, conducting the polymerization in wet hexanes, the fast polymerization of IB was retained in the presence of impurities with a slight decrease in exo‐olefin content. ¹H NMR studies suggest that nucleophilic impurities are protonated in the presence of water, and thereby neutralized. Mechanistic studies suggest that the rate constant of activation (k_a), rate constant of propagation (k_p), and rate constant of β‐proton elimination (k_tr) are not affected by the presence of impurities. To account for the retardation of polymerization in the presence of impurities, delay of proton transfer to monomer in the chain transfer step is proposed. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3697–3704     

Effect of chain structure on the glass transition temperature and viscoelastic property of cis‐1,4‐polybutadiene via molecular simulation

In this work, by adopting the united atom model of cis‐1,4‐poly(butadiene) (PB), we systemically investigate the effect of the chain structure on the glass transition temperature (T_g) and the viscoelastic property of PB system. First, we analyze the atom translational mobility, bond reorientation dynamics, torsional dynamics, conformational transition rate, and dynamic heterogeneity of the PB chains with different chain structures in detail by determining the corresponding T_g. In addition, our results clearly indicate that with the decrease of the amount of the free end atoms of PB via the end‐linking method, the mobility of the PB chains quickly decreases. As a result, the T_g of the PB chains gradually increases. Depending on the chain structure and the calculation method, the T_g of the PB chains varies from 154 to 240 K. In addition, the temperature dependence of the dynamic properties has different Arrhenius behaviors above and below T_g. The calculated activation energy varies from 7.37 to 16.37 KJ/mol for different chain structures above T_g, which can be compared with those for other polymers. In addition, through the end‐linking approach the strong interaction between the PB chains improves the storage modulus G′ and the loss modulus . Meanwhile, the immobility of the free end atoms effectively reduces the friction loss of the chains under the shear field, which is reflected by the low loss factor . In summary, this work can further help to understand the effect of the chain structure on the dynamic properties of the PB chains. Meanwhile, it provides an effective approach to reduce the energy loss during the dynamic periodic deformation, which can cut the fuel consumption via the end‐linking method. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1005–1016