A rare self-assembly behavior is observed in a hydrophilic monomer (4-vinylpyridine) (4VP) when polymerized in water with a hydrophilic initiator that results in the production of monodisperse polymeric nanoparticles in a single step. This behavior mimics the behavior obtained with the more commonly reported amphiphilic block copolymers. The synthesis and self-assembly of homopolymer nanoparticle from 4VP without the use of any cross-linker, stabilizing agent, surfactant, or polymeric emulsifier are described along with fundamental aspects of the mechanism of this polymerization. This facile and robust procedure enabled the production of highly monodisperse P4VP nanoparticle with a tunable size ranging from 80 to 445 nm. For the first time, we have investigated the growth mechanism of these polymeric nanoparticles to clarify the mechanism of polymeric nanoparticle formation. This work also provides direct visible evidence through transmission electron microscopy (TEM) images at the nanometer scale, which helps in obtaining a better understanding of the mechanism of self-assembly. The effect of temperature on the size of the polymeric nanoparticles was also examined along with the effect of initiator, monomer, and solvent concentrations. We therefore report a versatile and scalable process for the production of monodisperse polymeric nanoparticles, which we call self-emulsion polymerization (SEP).

The design of crystalline polymers is intellectually stimulating and synthetically challenging, especially when the polymerization of any monomer occurs in a linear dimension. Such linear growth often leads to entropically driven chain entanglements and thus is detrimental to attempts to realize the full potential of conjugated molecular structures. Here we report the polymerization of two-monomer-connected precursors (TMCPs) in which two pyrrole units are linked through a connector, yielding highly crystalline polymers. The simultaneous growth of the TMCP results in a close-packed crystal in polypyrrole (PPy) at the molecular scale with either a hexagonal close-packed or face-centred cubic structure, as confirmed by high-voltage electron microscopy, and the structure that formed could be controlled by simply changing the connector. The electrical conductivity of the TMCP-based PPy is almost 35 times that of single-monomer-based PPy, demonstrating its promise for application in diverse fields.

Molecular ordering of organic semiconductors comprising a newly designed A(D–A′–D)2 system was achieved through hydrogen bonding after removal of tert-butyloxycarbonyl substituents.

(E)-6,60 -Dibromo-1,1-bis(2-octyldodecyl)-(3,3 0 -biindolinylid-ene)-2,2 0 -dione and/or 2,5-bis(2-octyldodecyl)-3,6-di(5-bromothien-2-yl)pyrrolo [3,4-c]pyrrole-1,4-(2H,5H)-dione and their tBoc-counterparts were propagated with 2,5-bis(tributylstannyl)thiophene in a molar ratio of 0.8 : 0.2 : 1.0 to release P(ODIDT-BID), P(ODIDT$BDPP), P(ODDPPT$BID) and P(ODDPPT$BDPP) as a new series of random conjugated polymers (RCPs) bearing a large number of octyldodecyl chains to ensure solubility and a small number of thermocleavable tBoc function to cast H-bonding upon heating up to 220 C. All new polymers were synthesised via Pd catalysed Stille cross-coupling methodology in high yields and reasonable average molecular weights. The cast polymer films exhibited considerable red-shifted UV-vis absorption spectra and a further red-shift was also obtained in the thermal annealed films (at 220 C for 30 min), which reflected the increasing of crystalline structure. The formation of H-bonding in these polymers was investigated using X-ray diffractometry (XRD) measurements. The field-effect mobilities of these polymers were investigated in the configuration of bottom-gate and bottom-contact (BGBC) field-effect transistors (FETs). The results from FETs indicated that the crystalline structure of RCPs exhibited reasonable FET mobilities with 1.17 Â 10 À3 cm 2 V À1 s À1 for P(ODDPPT$BID) and 1.41 Â 10 À3 cm 2 V À1 s À1for P(ODDPPT$BDPP).

Considerable research approaches have focused on improving the crystallinity of conducting polymers to enhance the electrical conductivity. However, it is difficult to control the arrangement of polymer chains without the use of expensive and complex methods because of the intrinsic morphology of polymers. Herein, we report a one-step in situ process to produce controlled molecular-scale ordered polyaniline (PANI) films by coordination crosslinking with Zn ions using solvent-vapor thermal annealing (SVTA). The resulting PANI film crosslinked by Zn coordination has a face-centered cubic structure at the molecular scale, which was confirmed by high-voltage electron microscopy. The in situ coordination crosslinking produced a new class of molecular ordering in the PANI films and drastically enhanced their conductivity, showing their potential for use in various electronic and energy devices.