Sub-10 nm Scale Lamellar Structures with a High Degree of Long-Range Order Fabricated by Orthogonal Self-Assembly of Crown Ether/Secondary Dialkylammonium Recognition and Metal···Metal/π–π Interactions

Abstract

We here present an orthogonal self-assembly strategy to fabricate a series of metallosupramolecular polymers by coupling planar platinum(II) complexes and starlike poly(ε-caprolactone), through Pt•••Pt/π−π interactions and host−guest recognition between secondary dialkylammonium salts and crown ether groups. The solid metallosupramolecular polymers exhibit sub-10 nm scale lamellar structures and one of them occupies an extraordinary degree of long-range order. The platinum(II) complexes can be regarded as an individual supramolecular block to microphase segregate the polymeric segment. Moreover, the metallosupramolecular polymers show intense luminescence and appreciable proton conductivity, originating from these two supramolecular connection modes, respectively. This work paves the way for fabricating metallosupramolecular polymers showing both highly ordered nanostructures and multifunctional properties.

3,4-Ethylenedioxythiophene (EDOT) End-Group Functionalized Poly-ε-caprolactone (PCL): Self-Assembly in Organic Solvents and Its Coincidentally Observed Peculiar Behavior in Thin Film and Protonated Media

“…It has been explained that when such droplets form, their high surface tension prevents the crystallization of semicrystalline polymers; thus, it is difficult to make them have a lamellar morphology [ 86 ]. In our particular case, besides there being a reason similar to that mentioned above, the EDOT moieties’ intermolecular π–π aromatic interaction, in the inner core of the micelles, could also be an effective hindrance of the crystallization of the OCL shell, as was observed by others [ 87 ]. The morphology of the thin film obtained from the EDOT-PCL chloroform solution on mica is in stark contrast to that obtained previously for another PCL-containing macromonomer (2,5-dibromo-1,4-phenylene-PCL substituted) in Chl [ 88 ], which formed flat-on lamellae after spin-coating on a hydrophilized SiO2 surface (without any melting and recrystallization).…”

Fabrication of High χ-Low N Block Copolymers with Thermally Stable Sub-5 nm Microdomains Using Polyzwitterion as a Constituent Block

“…The central point to design high χ-low N BCPs is to find two polymers with quite different physical and chemical properties like surface energy, hydrophily hydrophobicity, and so on. Based on this principle, polymers containing fluorine, − silicon, − hydroxyl or amino groups, ,− carbonate groups, and crystalline/liquid crystalline structures − are frequently used as the constituent block of high χ-low N BCPs. However, above-mentioned polymers usually involve complicated monomer synthesis or polymerization.…”

Dimerization of sub-nanoscale molecular clusters affords broadly tuneable viscoelasticity above the glass transition temperature

“…Meanwhile, there is no obvious peak signal around 1.84 Å−1 (0.34 nm) corresponding to p-p stacking from the SAXS results, conrming the absence of strong supramolecular interaction. [31][32][33][34] The structure factor peak at 0.509 Å−1 characterizes the close packing of OPOSS (d) units from different dimer molecules, which is further conrmed by its consistency with that of the melt of pure OPOSS. The second peak in the low q range (0.161 to 0.173 Å−1 ), corresponds to the correlation length (z) of close packed zones of OPOSSs (Fig.…”