Well-defined polystyrene (PSt) or poly(ε-caprolacone (PCL) precursor polymers, possessing central or end 2,5-dibromo-1,4-phenylene, 2,5-dibromo-benzene or 3,5-dibromobenzene moieties, were synthesized by controlled polymerization methods, such as Atom Transfer Radical Polymerization (ATRP) or Ring Openining Polymerization (ROP). Further modification of these polymers in one or two reaction steps at the aromatic bromine atoms afforded bi-functionalized prepolymers. The first reaction step was a Suzuki coupling reaction between aromatic bromine functional polymers and 3-aminophenylboronic acid, yielding di-amino-containing intermediates. The second step was a condensation reaction between the di-amino functional intermediates and 4-(dimethylamino)-benzaldehyde. Thus, dimethyl-amino functional prepolymers were synthesized as well. The presence of amino or N, N′-dimethyl amino functional groups in the structure of intermediate polymers permitted co-polymerization with methyl methacrylate (MMA) by photoinduced radical polymerization by using benzophenone or Erythrosin B as photosensitizer and 4- or 3-armed star co-polymers (PSt-PMMA or PCL-PMMA) were obtained. The structures of all the starting polymers, intermediate polymers and final co-polymers were analyzed by spectral methods (1H-NMR, IR), as well as by GPC measurements. DSC analyses were performed for prepolymers and co-polymers and compared.

In the present work, we demonstrate that the side chain choice, as a tunable parameter, is an effective strategy to drive molecular ordering, packing motifs and overall microstructure of a conjugated polymer. By applying Wittig polycondensation novel ‘rod-coil’ structures, in ‘hairy-rod’ architecture, based on fluorenylene vinylene copolymers with well-defined oligomeric side chains were synthesized using ‘T’-shaped or ‘Cross’-shaped p-terphenyl macromonomers. The overall character of the copolymers was systematically varied by attaching of hydrophilic PEG 2000, hydrophobic polar oligo-ε-caprolactone or hydrophobic and non-polar oligostyrene side chains. Self-assembling of the copolymers by simple direct dissolution method was achieved in various solvents by modifying their selectivity in relation to the side chain or main chain. The morphology investigations demonstrated that unique nanofeatures obtained in each case (helical foldamers, vesicles, disks, or helical turns) depend on the nature, number, and position of the side chains which influence the photophysical properties. The ‘hairy-rod’ topology is also responsible for the self-assembly of the materials in molten state, as thermal analysis revealed, and the propensity of the new synthesized conjugated main chain for helical folding was evidenced, as well.

End-group functionalization of homopolymers is a valuable way to produce high-fidelity nanostructured and functional soft materials when the structures obtained have the capacity for self-assembly (SA) encoded in their structural details. Herein, an end-functionalized PCL with a π-conjugated EDOT moiety, (EDOT-PCL), designed exclusively from hydrophobic domains, as a functional “hydrophobic amphiphile”, was synthesized in the bulk ROP of ε-caprolactone. The experimental results obtained by spectroscopic methods, including NMR, UV-vis, and fluorescence, using DLS and by AFM, confirm that in solvents with extremely different polarities (chloroform and acetonitrile), EDOT-PCL presents an interaction- and structure-based bias, which is strong and selective enough to exert control over supramolecular packing, both in dispersions and in the film state. This leads to the diversity of SA structures, including spheroidal, straight, and helical rods, as well as orthorhombic single crystals, with solvent-dependent shapes and sizes, confirming that EDOT-PCL behaves as a “block-molecule”. According to the results from AFM imaging, an unexpected transformation of micelle-type nanostructures into single 2D lamellar crystals, through breakout crystallization, took place by simple acetonitrile evaporation during the formation of the film on the mica support at room temperature. Moreover, EDOT-PCL’s propensity for spontaneous oxidant-free oligomerization in acidic media was proposed as a presumptive answer for the unexpected appearance of blue color during its dissolution in CDCl₃ at a high concentration. FT-IR, UV-vis, and fluorescence techniques were used to support this claim. Besides being intriguing and unforeseen, the experimental findings concerning EDOT-PCL have raised new and interesting questions that deserve to be addressed in future research.

Because the combination of π-conjugated polymers with biocompatible synthetic counterparts leads to the development of bio-relevant functional materials, this paper reports a new oligo(2-methyl-2-oxazoline) (OMeOx)-containing thiophene macromonomer, denoted Th-OMeOx. It can be used as a reactive precursor for synthesis of a polymerizable 2,2’-3-OMeOx-substituted bithiophene by Suzuki coupling. Also a grafted polythiophene amphiphile with OMeOx side chains was synthesized by its self-acid-assisted polymerization (SAAP) in bulk. The results showed that Th-OMeOx is not only a reactive intermediate but also a versatile functional material in itself. This is due to the presence of 2-bromo-substituted thiophene and ω-hydroxyl functional end-groups, and due to the multiple functionalities encoded in its structure (photosensitivity, water self-dispersibility, self-assembling capacity). Thus, analysis of its behavior in solvents of different selectivities revealed that Th-OMeOx forms self-assembled structures (micelles or vesicles) by “direct dissolution”.Unexpectedly, by exciting the Th-OMeOx micelles formed in water with λ_abs of the OMeOx repeating units, the intensity of fluorescence emission varied in a concentration-dependent manner.These self-assembled structures showed excitation-dependent luminescence as well. Attributed to the clusteroluminescence phenomenon due to the aggregation and through space interactions of electron-rich groups in non-conjugated, non-aromatic OMeOx, this behavior certifies that polypeptides mimic the character of Th-OMeOx as a non-conventional intrinsic luminescent material.

The development of the modern society imposes a fast-growing demand for new advanced functional polymer materials. To this aim, one of the most plausible current methodologies is the end-group functionalization of existing conventional polymers. If the end functional group is able to polymerize, this method enables the synthesis of a molecularly complex, grafted architecture that opens the access to a wider range of material properties, as well as tailoring the special functions required for certain applications. In this context, the present paper reports on α-thienyl-ω-hydroxyl-end-groups functionalized oligo-(D,L-lactide) (Th-PDLLA), which was designed to combine the polymerizability and photophysical properties of thiophene with the biocompatibility and biodegradability of poly-(D,L-lactide). Th-PDLLA was synthesized using the path of “functional initiator” in the ring-opening polymerization (ROP) of (D,L)-lactide, assisted by stannous 2-ethyl hexanoate (Sn(oct)₂). The results of NMR and FT-IR spectroscopic methods confirmed the Th-PDLLA’s expected structure, while the oligomeric nature of Th-PDLLA, as resulting from the calculations based on ¹H-NMR data, is supported by the findings from gel permeation chromatography (GPC) and by the results of the thermal analyses. The behavior of Th-PDLLA in different organic solvents, evaluated by UV–vis and fluorescence spectroscopy, but also by dynamic light scattering (DLS), suggested the presence of colloidal supramolecular structures, underlining the nature of the macromonomer Th-PDLLA as an “shape amphiphile”. To test its functionality, the ability of Th-PDLLA to work as a building block for the synthesis of molecular composites was demonstrated by photoinduced oxidative homopolymerization in the presence of diphenyliodonium salt (DPI). The occurrence of a polymerization process, with the formation of a thiophene-conjugated oligomeric main chain grafted with oligomeric PDLLA, was proven, in addition to the visual changes, by the results of GPC, ¹H-NMR, FT-IR, UV–vis and fluorescence measurements.

In the field of advanced functional materials, π-conjugated, electrically conductive polymers (CPs) represent a highly specialized class, intensively studied as essential in contemporary optoelectronic and biointerfaced technologies. The solution-processability of CPs represents a significant advantage; however, the interactions occurring in this state make it difficult to establish suitable strategies for controlling the resulting solid-state microstructures and the charge transport. In this context, the main aim of this paper was to analyze how the polymer architecture and other deliberately chosen design criteria, can be harnessed and easily combined with a versatile processing toward self-assembled thin films of varying surface properties. Thus, a “rod-graft-coil” polymacromonomer, denoted OTh-PDLLA,—previously synthesized via metal-free-photoinduced oxidative polymerization, yielding an oligomeric structure comprising a π-conjugated thiophene backbone with densely grafted oligo(D,L-lactide) side chains—was processed into thin films by drop-casting, in native and also in its LiClO₄-treated form, on rigid glass slides and on flexible polylactide (PLA) sheets, using solvents of differing quality, at various concentrations. The influence of these processing parameters on the shape and size of the formed self-assembled supramolecular structures on films surface was analyzed, and the processing-dependent surfaces wettability changes were also discussed.