Close-packed polymer crystals from two-monomer-connected precursors

Abstract

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.

Nanocomposite Supercapacitor Electrode from Sulfonated Graphene Oxide and Poly(pyrrole-(biphenyldisulfonic acid)-pyrrole)

“…The crystalline polymers have a small surface area and high packing fraction, similar to our polymers, without SGO, as shown in the BET results. The surface area of the well-ordered polymer nanocomposite (61 m 2 g –1 ) is increased 3-fold compared to that of the pure polymer (19 m 2 g –1 ), showing the significant role of SGO sheets in enhancing the surface area (Figure S4).…”

“…The ordered structure of the nanocomposite is visible in Figure a. The electron diffraction pattern in the HRTEM image pertains to high electron density clusters for pyrrole and sulfonated graphene oxide, unlike that of the surrounding carbon atoms . Hence, we infer that these high electron density clusters of P­(Py:BPDSA:Py) were grown at the nanoscale on the SGO sheets.…”

“…The synthesis of modified conducting polymers has been achieved by introducing suitable regioregular substituents and suitable side chains. − Various methods of synthesis to generate highly ordered polymer films have been achieved. − Regardless of these efforts, the synthesis of well-ordered polymers still has many challenges. We have already reported that by utilizing cross-linking and polymerization of two-monomer-connected precursors (TMCPs, Py:BPDSA:Py), such a well-ordered polymer structure can be easily synthesized. , The electrical conductivity of the ordered polymers is sufficiently high for the SC electrode; however, the ion penetration is hindered due to its low surface area and compact structures …”

Engineering crystalline quasi-two-dimensional polyaniline thin film with enhanced electrical and chemiresistive sensing performances

“…It is well known that structural disorder hinders efficient charge transport in conducting polymer films 8,9 , thus degrades device performance. To achieve long-range charge transport, one promising strategy is to align the linear conducting polymer chains into quasi-two-dimensional (q2D) crystalline films 10,11 . The q2D film, composed by highly ordered supramolecular assembly of molecules/polymers with fully expanded-coil conformation via interchain interactions 12–14 , can provide multiple pathways for interchain charge transport 8,9 and bypass possible defects of individual polymer chains 15 .…”

Synthesis of Reactive Water-Soluble Narrow-Band-Gap Polymers for Post-Crosslinking

“…However, the stability of the thin films in the devices using electrolyte solutions are poor due to resolubilization. Post-crosslinking is important for preventing resolubilization and preparing electron conducting routes between the polymer chains [24,25]. Herein, we demonstrate the synthesis of reactive water-soluble narrow-band-gap polymers for post-crosslinking.…”