Journal of Polymer Science Part A: Polymer Chemistry

The rapidly progressing field of organic electronics research has inspired a renaissance in the chemistry of dye molecules, compelling scientists to revitalize historical pigments, transform them into soluble dyes, and apply them in the construction of advanced macro(molecular) semiconducting materials. The Highlight by M. J. Robb et al. on page 1263 explores the resurgence of notable building blocks including diketopyrrolopyrrole (DPP), (iso)indigo, benzodipyrrolidone, and benzodifuranone, as well as the non-fullerene acceptor structures 9,9'-bifluorenylidene (99BF) and quinacridone shown here. Their outstanding characteristics and synthetic availability have led to cutting-edge materials with remarkable properties well-suited for organic electronic devices.

As presented by Marta Fernández-García et al. on page 1337, two series of amphiphilic di- and triblock glycopolymers obtained by controlled radical polymerization directly using an unprotected glycomonomer are displayed. Some of these block glycopolymers, depending on the length of hydrophilic segment, can be water soluble and then self-aggregate as micelles. In addition to these solution properties, they can specifically bind with Concanavalin A lectin. It is important to mention that those block glycopolymers based on poly(methyl methacrylate) (PMMA) seem to be more suitable to this lectin than those with poly(n-butyl acrylate) (PBA).

The need for higher performance organic electronic materials has inspired a resurgence of historical dyes and pigments and their transformation into new families of π-conjugated building blocks used to construct advanced (macro)molecular semiconductors. Their outstanding properties and synthetic availability have led to cutting-edge materials with remarkable properties well-suited for organic electronic devices. These building blocks are now being used to assemble the next generation of electronic materials with precise structure and function.

A new synthetic strategy to prepare dendrimers using a single, inexpensive monomer is described. Divergent growth relies on a highly efficient, metal-free Click cycloaddition of azides to alkynes. Functional dendrimers are obtained with minimal purification in high yields, with no by-product but a water soluble salt, and the excess of monomer used can be recycled at each stage of the iterative synthesis.

Molecular weight and microstructure controlled poly(N-cyclohexyl-5-norbornene-2,3-dicarboximide)s have been synthesized through ring opening metathesis polymerization. These materials were employed as electro-optic (EO) polymer hosts for high molecular hyperpolarizability chromophores. Polymer having 98% trans microstructure exhibited enhanced EO activity after poling at elevated temperatures, showing an EO coefficient of 93 pm/V. Temporal stability of EO activity was confirmed due to the high-T_g property of the polymer host.

Two new dihydropyrroloindoledione-based copolymers were designed, synthesized, and characterized. The synthesis is two-directional throughout with a Pummerer-type cyclization as the key step to form the core tricycle. The polymers have very good solubility in organic solvents, broad UV-optical absorption, and a HOMO energy level of −5.47 eV. Computational modeling validates the increase in bandgap as the thiophene comonomer is changed to phenyl, inducing slight torsional twisting along the near planar polymer backbone.

Functional polynorbornenes containing pyrrolidine moiety and bis(trifluoromethyl)biphenyl side group were synthesized by ring-opening metathesis polymerization. Pyrrolidine-contained PTNP and PPNP are supposed to have practically trans double bonds and adopt isotactic syn conformation, whereas dicarboximide type PTNDI has both trans and cis double bonds and atactic microstructure. PTNP possessing a polar 3,5-bis (trifluoromethyl)biphenyl group and the stereoregular chain structure displays a more attractive dielectric constant value (over 20) than those of PTNDI (about 7) and PPNP (only 3).

High-performance functional polyimides with fluorescent and resistive switching (ON–OFF) characteristic were synthesized by introduction of aromatic rigid nonplanar conjugated tetraphenylethylene moieties into the polyimide main chain.

Optically active poly(m-phenylene)s substituted with chiral oxazoline derivatives have been synthesized by the nickel-catalyzed Yamamoto coupling reaction of optically active (S)-4-benzyl-2-(3,5-dihalidephenyl)oxazoline derivatives. The optical activities of the polymers should be attributed to the higher order structure such as helical conformations. Moreover, the helical conformation could be induced by addition of metal salts into polymer solutions. The polymers showed good thermal stabilities, which was attributable to the oxazoline side chains.

The decomposition mechanism and kinetics of SG1-based alkoxyamines (R = Me, tBu, Et, H) at different conditions have been studied. The possible side reactions that alter NMP have been evaluated. It has been shown that H-transfer reaction occurs during the decomposition of three alkoxyamines in highly degassed solution, except for SG1-MAMA. The decomposition in poorly degassed solution reveals the high impact of oxygen on the decomposition mechanism. The acidity of the reaction medium affects the decomposition mechanism suppressing the H-atom transfer.

Two different amphiphilic block glycopolymer series based on n-butyl acrylate and methyl methacrylate with2-{[(D-glucosamin-2-N-yl)carbonyl]oxy}ethyl acrylate were synthesized by single-electron transfer-living radical. The glycopolymer formation is favored when poly(methyl methacrylate) macroinitiators were used. Well-controlled and water soluble glycopolymers were able to self-aggregate into micelles and specifically bind with Concanavalin A lectin.

Three types of random copolyimides containing perylenebisimide, naphthalenebisimide, and pyromelliticbisimide were designed and synthesized to evaluate the effects of the acceptor conjugation length and composition on the electrical memory characteristics.

Ionic networks linked by ammonium carboxylates can be prepared by simple mixing of balanced ratios of dendritic amines and carboxylic acid end-functionalized poly(ethylene glycol)s. The networks have a high thermal stability and are suggested to be employed in the development of novel polymeric materials with self-healing properties.

The reactivity ratios for the copolymerization of a first-generation dendronized monomer with styrene and different acrylates are determined. The obtained ratios as well as the copolymer compositions that can be expected are discussed in detail. The influence of the dendron on the polymerization potential of the monomer is estimated by comparing its reactivity to those of linear systems as well as using higher generations of the dendronized monomer.

Sixteen different sequential interpenetrating network (SeqIPN) hydrogels based on purely PEG systems were efficiently fabricated via UV initiated thiol-ene coupling chemistry. These covered both loosely (8 kDa) as well as densely crosslinked (2 kDa) systems and capitalized on determining the impact of diffusion time of secondary network precursors on the final swelling and mechanical properties of SeqIPNs. The results within detail the power of diffusion time as an imperative parameter to accurately control the final properties of SeqIPN hydrogels based on PEG systems.

Poly(isosorbide carbonate) was synthesized by melt polycondensation of dimethyl carbonate and isosorbide using lithium acetylacetonate as the catalyst. The reaction conditions were optimized. A series of poly(aliphatic diol-co-isosorbide carbonate)s were also synthesized by melt polycondensation of DMC with isosorbide and equimolar amounts of aliphatic diols (1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,4-cyclohexane dimethanol) in the presence of LiAcac and the TiO₂/SiO₂-based catalyst (TSP-44).

A styrene-based monomer having a five-membered cyclic dithiocarbonate structure 4-vinylbenzyl 1,3-oxathiolane-2-thione-5-ylmethyl ether (VBTE) was prepared by addition of carbon disulfide to 4-vinylbenzyl glycidyl ether. Polymerization of the VBTE readily proceeded using 2,2′-azobisisobutyronitrile as an initiator to give polyVBTE.

β-Cyclodextrins were bonded to the branch points of a H-shaped copolymer. The attachment of β-cyclodextrin caused the self-assembly of the H-shaped polymer in water at 25 °C. The formed micelles transformed into smaller ones when temperature was above the lower critical solution temperature of the polymer.

Water-soluble PT-g-PMeO₂MA (PTD) and PT-g-P(MeO₂MA-co-OEGMA) (PTDO) are synthesized using ATRP. The PT-chains self-organize as nanospheres, being surrounded by PMeO₂MA fibers producing miceller aggregates. A sharp increase of Z-average particle size of PTD solution with temperature occurs at LCST, which increases with OEGMA concentration in PTDO. The temperature dependent PL emission of PTD shows minimum at 19 °C, followed by a sharp increase and with increasing OEGMA concentration in PTDO copolymers, the hike occurs at progressively higher temperatures.

This work describes a simple and fast procedure to synthesize a water soluble 3D macromolecular box, having four porphyrin units as walls, and its Cobalt derivative. Their chemical and spectroscopic characterization was performed by means of MALDI-TOF-MS, NMR, CD, and UV–vis spectroscopy. The molecular structure of these systems suggests their use as nanoscopic molecular boxes, able to incorporate giant molecular species. Preliminary experiments about the host/guest complex formation between these cycles and Gramicidin S have been here discussed.

New ω-alkenyl-substituted ansa-bridged zirconium complexes are tested as self-immobilized catalysts for ethene polymerization. While the corresponding ligands are shown to be suitable comonomers for ethene, and innovative copolymers are prepared and characterized by ¹³C NMR spectroscopy, even under the most favourable conditions or by “cross polymerization” using rac-Me₂Si(2-MeBenzInd)₂ZrCl₂ (MBI), there is no evidence of their insertion into the polymer chain.

Poly(I-proline) (PLP) in the form II has been used for the facile synthesis of gold nanoparticles in water. The PLP had a dual role, as a reductant and a stabilizer of the formed Au nanoparticles (Au-NPs). The experimental conditions required for the formation of the Au-NPs has been thoroughly investigated. The nanoparticles obtained were among the smallest presented so far by polymeric materials. The mechanism of the formation of the Au-NPs has also been shown by various methods.

New poly(2,5-bis(2-octyldodecyl)-3-(5-(pyren-2-yl)thiophen-2-yl)-6-(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione) (P(DTDPP-alt-(2,7)PY)) was successfully synthesized via Suzuki coupling reactions. An organic thin-film transistor fabricated using the newly synthesized P(DTDPP-alt-(2,7)PY) exhibited a maximum mobility of up to 0.23 cm² V^–1 s^–1 (I_on/off ∼ 10⁶) as a semiconductor material. In addition, the OPT devices made of P(DTDPP-alt-(2,7)PY) showed interesting photoinduced enhancement of drain current when irradiating with the excitation light whose intensity is very low.

Zn(0)/CuBr₂ (where CuBr₂ concentrations are in the range of 10–50 ppm) was firstly used to catalyze radical polymerization of acrylonitrile at ambient temperature. The polymerization displayed typical living radical polymerization characteristics, as evidenced by pseudo first-order kinetics of polymerization, linear increase of number-average molecular weight, and low polydispersity index value.