Polymer Main Chain Research Articles

Facile Preparation of High-Performance Polythiophene Derivative and Effect of Torsion Angle Between Thiophene Rings on Electrochromic Color Change.

The electrochromic phenomenon of conducting polymer is mainly dominated by the π-π* band transition. The π conjugation is influenced by the coplanarity between polymer units, deviations from which can lead to an increased ionization potential and band gap values. In order to investigate the effect of plane distortion angle on electrochromic color in the main chain structure of polymerization, high-performance poly(3,3'-dimethyl-2,2'-bithiophene) (PDMeBTh) with a large plane distortion angle is successfully synthesized in boron trifluoride diethyl etherate (BFEE) by the electrochemical anodic oxidation method. The electrochemical and thermal properties of PDMeBTh prepared from BFEE and ACN/TBATFB are compared. The electrochromic properties of PDMeBTh are systematically investigated. The PDMeBTh shows a different color change (orange-yellow in the neutral state) compared to poly (3-methylthiophene) (light-red in the neutral state) due to the large torsion angle between thiophene rings of the main polymer chain. The optical contrast, response time, and coloring efficiency (CE) of the prepared PDMeBTh are also studied, which shows good electrochromic properties. For practical applications, an electrochromic device is fabricated by the PDMeBTh and PEDOT. The color of the device can be reversibly changed between orange-yellow and dark blue. The light contrast of the device is 27% at 433 nm and 61% at 634 nm. The CE value of the device is 403 cm2 C-1 at 433 nm and 577 cm2 C-1 at 634 nm. The constructed device also has good open circuit memory and electrochromic stability, showing good potential for practical applications.

Luminescent Radical Polymers.

Organic radicals are gaining significant interest in luminescent materials due to their unique properties, which present unprecedented opportunities for innovation across various fields, from display technology to biomedical applications. However, addressing challenges related to stability and low fluorescence efficiency is crucial to unlocking their full potential for practical applications. Polymerization has emerged as an effective strategy to enhance intra- and interchain through-space interactions, enabling the creation of stable luminescent radicals with excellent processing and multifunctional properties. This concept emphasizes the strategic use of polymerization in designing and synthesizing stable main-chain and side-chain radical polymers. This approach not only broadens the scope of stable radicals but also improves their luminescence properties as photofunctional materials.

Radical Copolymerization of 2‐Thiocyanatoethyl Substituted Acrylate to Introduce Thiol‐Acrylate‐Based Dynamic Bonds as Degradable Linker

ABSTRACTWe employ the 1,4‐cyano group migration radical polymerization strategy to copolymerize acrylates with 2‐thiocyanate ethyl substituted acrylates. The radical copolymerization can be effectively controlled using reversible addition−fragmentation chain‐transfer (RAFT) polymerization. This approach can incorporate thiol‐acrylate‐based dynamic bonds within the polymer main chain. Utilizing these dynamic bonds, we degrade the polymers under mild basic conditions, achieved with the assistance of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) to facilitate the reversible thiol‐Michael addition. Notably, high degradation efficiency is observed. This study exemplifies the application of 2‐thiocyanate ethyl substituted acrylate in radical copolymerization to produce degradable polymers.

Dinickel-Catalyzed N=N Coupling Reactions for the Synthesis of Hindered Azoarenes.

Azoarenes are the largest class of photoswitching molecules, and they have a broad range of applications in photopharmacology and materials science. Azoarenes possessing ortho-substitution often display improved properties, including isomerization under visible light irradiation, near-quantitative switching, and long thermal half-lives in the cis form. The synthesis of hindered ortho-substituted azoarenes is often low-yielding using established oxidative or reductive coupling methods. Here, we describe the design and synthesis of a new dinickel complex that catalyzes the dimerization of ortho-substituted aryl azides in high yield. Applications of this method in the synthesis of high-performance photoswitches, photoactive peptide cross-linkers, hindered diazocines, and main-chain azoarene polymers are described.

Soft hydrogels obtained by photothermal curing of poly(vinylpyrrolidone)/gold nanoparticles dispersions showing anisotropic swelling and photo-activated antimicrobial properties

Poly(vinylpyrrolidone) (PVP) hydrogels were obtained by green light irradiation of aqueous PVP/ammonium persulfate solutions modified with gold nanoparticles (AuNPs). The increase in temperature produced through the activation of the photothermal effect of AuNPs triggers the decomposition of ammonium persulfate producing radicals that, by attacking the polymer main chain and generating macro-radicals, induce the crosslinking of the polymer via recombination paths. Irradiation from the top of the solutions in an open configuration produced water evaporation and a concomitant increase in temperature during curing, giving rise to dry materials with high aspect ratio and moderate swelling anisotropy. Pads that reversibly adhere to different substrates, including human skin, were produced by simple contact of the final materials with water. Impregnation of gauze wound dressings with PVP-Au-ammonium persulfate dispersions, followed by direct “in situ” photothermal crosslinking, enabled the fabrication of supported functional pads with potential applications as reversible adhesive skin wound dressings. Infusion of the hydrogels with Rose Bengal (RB) provides the materials with photosensitizing properties useful for the photodynamic inactivation of Staphylococcus aureus. A decrease in cell viability of 99.9% was attained after 30 min of irradiation with a low-power green LED source, which demonstrates the efficient singlet oxygen production by RB in the hydrogels and paves the way towards the design of new stimulus-activated bactericidal supplies for biomedical uses.

Chlorinated Polythiophene‐Based Donors with Reduced Energy Loss for Organic Solar Cells

Comprehensive SummaryThe industrialization of organic solar cells (OSCs) faces challenges due to complex synthesis routes and high costs of organic photovoltaic materials. To address this, we designed and synthesized a series of polythiophene‐based donor materials, PTVT‐T‐xCl (20%Cl, 50%Cl and 100%Cl), by introducing different degrees of chlorine substitution within their conjugated skeletons. The incorporation of chlorine atoms does not change the planar conformation of the conjugated main chain of the control polymer, PTVT‐T, but effectively reduces their HOMO energy levels (≤ –5.3 eV) and alters the crystallinity of the polymers. In addition, when preparing OSC by blending with non‐fused electron acceptor A4T‐16, the non‐radiative energy loss of the three photovoltaic devices gradually decreased with the increase of chlorine content (0.343, 0.278 and 0.189 eV, respectively). Notably, PTVT‐T‐20%Cl exhibited a more moderate nanoscale phase separation with the acceptor, leading to efficient exciton dissociation, lower bimolecular recombination, and thus a favorable current in the OSCs. Consequently, the photovoltaic device based on PTVT‐T‐20%Cl:A4T‐16 achieved a remarkable photovoltaic efficiency of 11.8%. In addition, the PTVT‐T‐xCl series polymers show much lower material‐only‐cost (MOC) values than the other reported photoactive material systems. This work provides the way for the development of low‐cost photovoltaic materials and the industrial application of OSC, overcoming previous limitations posed by high energy losses in polythiophene‐based donors.

Polyethylene Materials with Tunable Degradability by Incorporating In-Chain Mechanophores.

Polyolefins are recognized as fundamental plastic materials that are manufactured in the largest quantities among all synthetic polymers. The chemical inertness of the saturated hydrocarbon chains is crucial for storing and using polyolefin plastics, but poses significant environmental challenges related to plastic pollution. Here, we report a versatile approach to creating polyethylene materials with tunable degradability by incorporating in-chain mechanophores. Through palladium-catalyzed coordination/insertion copolymerization of ethylene with cyclobutene-fused comonomers, several cyclobutane-fused mechanophores were successfully incorporated with varied insertion ratios (0.35-26 mol %). The resulting polyethylene materials with in-chain mechanophores exhibit both high thermal stability and remarkable acid resistance. Upon mechanochemical activation by ultrasonication or ball-milling, degradable functional units (imide and ester groups) are introduced into the main polymer chain. The synergy of mechanochemical activation and acid hydrolysis facilitates the efficient degradation of high molecular weight polyethylene materials into telechelic oligomers.

Thermoresponsive supramolecular nanocontainers from ionic complexes of amphiphilic wedge-shaped mesogens and polybases

Multi-responsive polymeric nanocontainers attract significant attention for their potential applications in biotechnology, drug delivery, catalysis, and other fields. By incorporating a liquid-crystalline (LC) mesogenic ligand with an alkyl tail length ranging from 8–12 carbons, ionically linked to the polymer backbone, we generate vesicles with walls significantly thinner than those of conventional polymersomes, approaching the thickness of a lipid bilayer. These LC vesicles, ranging in size from 50–120 nm, are designed to be mechanically robust due to the alignment of the hydrophilic polymer backbone within the plane of the vesicle wall. Additionally, incorporating a temperature-sensitive block into the polymer structure imparts thermoresponsiveness to the nanocontainers, enhancing their functionality and adaptability for various applications. Ionic complexes of hydrophilic polybases, specifically poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and PDMAEMA-b-PNIPAM (poly(N-isopropylacrylamide)) block copolymers, with amphiphilic wedge-shaped mesogens bearing a sulfonic acid group at the focal point were synthesized. The designed nanocontainers, in the form of either vesicles or nanotubes, exhibit a well-defined wall thickness of 5 nm, dictated by the organization of a smectic LC phase. The constructed coarse-grained models elucidate the mechanism of self-assembly, demonstrating that the balance between the hydrophilicity of the main polymer chain and the hydrophobicity of the wedge-shaped pendant groups determines both the internal and external structure of the vesicles.

Design of pH/Redox Co-Triggered Degradable Diselenide-Containing Polyprodrug via a Facile One-Pot Two-Step Approach for Tumor-Specific Chemotherapy.

The diselenide bond has attracted intense interest for drug delivery systems (DDSs) for tumor chemotherapy, owing to it possessing higher redox sensitivity than the disulfide one. Various redox-responsive diselenide-containing carriers have been developed for chemotherapeutics delivery. However, the premature drug leakage from these DDSs was significant enough to cause toxic side effects on normal cells. Here, a pH/redox co-triggered degradable polyprodrug was designed as a drug self-delivery system (DSDS) by incorporating drug molecules as structural units in the polymer main chains, using a facile one-pot two-step approach. The proposed PDOX could only degrade and release drugs by breaking both the neighboring acid-labile acylhydrazone and the redox-cleavable diselenide conjugations in the drug's structural units, triggered by the higher acidity and glutathione (GSH) or reactive oxygen species (ROS) levels in the tumor cells. Therefore, a slow solubility-controlled drug release was achieved for tumor-specific chemotherapy, indicating promising potential as a safe and efficient long-acting DSDS for future tumor treatment.

Controlling curcumin/acrylic polymer interactions for tailored delivery systems

In this work, we investigate the interaction between curcumin and biocompatible polymethacrylates (methyl, ethyl, and n-butyl side groups). Blend samples were produced using the salt leaching technique to increase the contact area in the ionic medium with pH 2.0, 5.0, 7.4, and 8.0. Using curcumin photoluminescence (PL) spectra to determine release profiles, we found a 6-fold higher quantity and a 3-fold higher release ratio for poly(n-butyl methacrylate) (PnBMA). Changes in the ionic form of curcumin were observed with PL blue shift and decrease in the characteristic time, from ca. 435 min at pH 2.0 and 5.0 to 192 min at pH 7.4 for PnBMA. The relative importance of curcumin interactions with the side and main polymer chains could be determined by interpreting the release profiles. With curcumin interaction controlled by pH and the length of the polymer side chain, one may envisage tailored drug delivery systems focusing on prolonged release.

Post-Functionalization of Thiophene-Fluorene Alternating Copolymers via Anodic Phosphonylation

Phosphonylated polymers are promising materials because of their application in sensor chemistry and their unique electronic properties. Among these polymers, conjugated polymers containing dialkylphosphonate at their side chains have been used in chemical sensors1 and exhibit unique electronic properties.2 However, there have been a few reports on phosphonylation into the conjugated polymer main chains except for poly(3-hexylthiophene) (P3HT)3 and polyaniline derivatives,4 demonstrating that the effect of phosphonate on their main chains has been unclear. To introduce the phosphonate into their main chains, electrochemical post-functionalization is an attractive approach because of the simple protocol and mild reaction conditions.5 Recently, anodic phosphonylation of P3HT at the main chains with trialkyl phosphite was reported.3 However, the applicable precursor polymer is limited to P3HT. Furthermore, the substitution degree was quite low (0.25), indicating that it is necessary to be improved for establishment.Here, to expand applicable precursor polymers and improve the substitution degree, anodic phosphonylation of thiophene–fluorene alternating copolymers (P(Fl-Th)) was conducted (Figure 1), and then we obtained the phosphonylated conjugated polymer (P(Fl-Th-phos(Et)) (substitution degree: 0.26). The obtained polymer showed that phosphonate was introduced selectively into electron-rich thiophene rings. However, the substitution degree was still low. When a 2,6-lutidine was added to the reaction solution, the substitution degree was increased up to 0.83. Furthermore, the substitution degree could be controlled by tuning the amount of charge passed, and the optoelectronic properties of P(Fl-Th-Phos(Et)) were gradually changed through control of the substitution degree. In addition, it was found that various trialkyl phosphite were available in anodic phosphonylation.To functionalize the fluorene units, we carried out anodic phosphonylation of P(Fl-EDOT) which was di-substituted at thiophene moieties, and then the degree of phosphonylation reached 0.75 under the constant-current condition. On the other hand, when we performed constant-potential anodic phosphonylation of P(Fl-EDOT), the substitution degree was improved up to 0.98, indicating that the use of constant-potential electrolysis enabled quantitative anodic phosphonylation.These results demonstrate that anodic phosphonylation can be applied to versatile π-conjugated polymers and that the position of phosphonate introduction can be controlled through the design of appropriate precursor polymers. In addition, due to two alkyl chains, the phosphonate group could enable further modification such as side-chain engineering of conjugated polymers.References G. Zhou, G. Qian, L. Ma, Y. Cheng, Z. Xie, L. Wang, X. Jing, F. Wang, Macromolecules, 2005, 38, 5416–5424.J. Hopkins, K. Fidanovski, L. Travaglini, D. Ta, J. Hook, P. Wagner, K. Wagner, A. Lauto, C. Cazorla, D. Officer, D. Mawad, Chem. Mater., 2022, 34, 140–151.K. Taniguchi, T. Kurioka, N. Shida, I. Tomita, S. Inagi, Polym. J., 2022, 54, 1171–1178.T. Amaya, I. Kurata, Y. Inada, T. Hatai, T. Hirao, RSC Adv., 2017, 7, 39306–39313.T. Kurioka, S. Inagi, Chem. Rec., 2021, 21, 2107–2119. Figure 1

Bio-based polyurethane vitrimer with imine bonds: Excellent thermo-mechanical properties and heat recovery

Preparation of vitrimer with excellent performance from biomass feedstock can effectively reduce the waste of fossil fuels and the pollution problem to the environment. In this paper, vanillin (VAN) and 4-amino-3-methylphenol, which are biobased raw materials, were used to prepare the imine-bonded diol AMV-OH in a one-step process, which was incorporated into the main chain of vitrimer polymer, and a series of imine-bonded vitrimer materials AMV-V was obtained by using pentaerythritol tetra-3-mercaptopropionate (PETMP) as a cross-linking agent. The mechanical property analysis, solvent resistance analysis, DSC thermal analysis, DMA analysis and self-repair characterization showed that AMV-V exhibited good thermo-mechanical properties (the highest initial degradation temperature was 246 °C with a Tg value of 17 °C). The results showed that specific mechanical properties could be obtained by adjusting the contents of PETMP and AMV-OH, among which the best tensile properties were obtained at 10 mmol of AMV-OH, with a tensile strength of 8.03 MPa and an elongation at break of 316.79 %. Meanwhile, the AMV-V samples were able to achieve self-healing properties under milder conditions (100 °C, 10 MPa repair for 1 h) and had a high self-healing efficiency (H=94.80 %, R=83.72 %).

Plenty of Space in the Backbone: Radical Ring-Opening Polymerization.

Radical polymerization is the most widely applied technique in both industry and fundamental science. However, its major drawback is that it typically yields polymers with non-functional, non-degradable all-carbon backbones-a limitation that radical ring-opening polymerization (rROP) allows to overcome. The last decade has seen a surge in rROP, primarily focused on creating degradable polymers. This pursuit has resulted in the creation of the first readily degradable materials through radical polymerization. Recent years have witnessed innovations in new monomers that address previous design limitations, such as ring strain and reactivity ratios. Furthermore, advances in integrating rROP with reversible deactivation radical polymerization (RDRP) have facilitated the incorporation of complex, customizable chemical payloads into the main polymer chain. This short review discusses the latest developments in monomer design with a focused analysis of their limitations in a broader historical context. Recently evolving strategies for compatibility of rROP monomers with RDRP are discussed, which are key to precision polymer synthesis. The latest chemistry surveyed expands the horizon beyond mere hydrolytic degradation. Now is the time to explore the chemical potential residing in the previously inaccessible polymer backbone.

Rapid synthesis and post-polymerization modification of poly(vinylene sulfide) via sequential nucleophilic thiol-yne/ene click reactions

Click chemistry has emerged as a versatile and robust polymerization technique for the construction of functional polymers. In this work, organocatalyst-mediated consecutive thiol-yne and thiol-ene click reactions were performed for the synthesis and modification of the electron-deficient poly(vinylene sulfide) (PVS) structure. PVS was prepared within an hour in the presence of 1,4-diazabicyclo[2.2.2] octane (DABCO) and in an anti-Markovnikov fashion, with a high molecular weight (M n = 12.9 kDa) and high stereoregularity (88% E-isomer). Following various optimization studies using 1-propanethiol as the model thiol, the obtained PVS was modified with various thiols in chloroform for 10 min using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as the catalyst, resulting in thioacetal main chain polymers. The scope of thiols used in the modification studies spans from alkyl and cycloalkyl to aromatic and allylic, and the polymers were obtained with varying efficiencies. Primary alkyl and aromatic thiols exhibited high efficiencies ranging from 87% to 100%. Similar high efficiencies were found for secondary mercaptans (70% and 92%); however, a very low efficiency (5%) was found for a tertiary mercaptan due to steric hindrance. It is believed the proposed indirect polythioacetal synthesis method holds the potential to be utilized in bio-related applications and material science.

Modulation of π-Conjugation of Polymer Main Chain Containing π-Extended Benzoxaborin by Molecular Addition

Modulation of π-Conjugation of Polymer Main Chain Containing π-Extended Benzoxaborin by Molecular Addition

Optically transparent and refractive thiol‐ene polymers containing cyclotriphosphazenes

AbstractA colorless, transparent thiol‐ene polymer network was developed that contains cyclic phosphazene units in the polymer chain. Hexakis (allyloxy) cyclotriphosphazene (HAP) was synthesized from the nucleophilic substitution reaction of phosphonitrilic chloride trimer and allyl alcohol. Thiol‐ene polymers (HAP‐SH) were successfully prepared without by‐products or the use of solvents through photopolymerization of the HAP and multithiol monomers with various functional group and flexible structures (e.g., 1,4‐butanedithiol (BDTH), 1,3,5‐benzenetrithiol (BTTH), trimethylolpropane tris (3‐mercaptopropionate) (TTMP) and pentaerythritol tetrakis (3‐mercaptopropionate) (PTTH)). The prepared HAP‐SH polymers showed sufficient thermal stability due to the high degree of cross‐linking. In addition, the HAP‐SH polymer films exhibited high optical transparency of over 90% in the visible region. The refractive indices of the HAP‐SH polymers measured at 637 nm were in the range of 1.5530–1.6344, and the Abbe number was calculated to be in the range of 34.5–47.1. These results are attributed to the structure of the cyclophosphazine and the polymer main chain containing aliphatic linkers with sulfur atoms. Another significant result was the transparency of the HAP‐SH polymer films in the mid‐infrared (MWIR) region. The thermal stability and excellent optical properties of the HAP‐SH polymers make them good candidates for application as a protective film for IR lenses, which are easily damaged by external factors.

Single‐step preparation of intrinsic solid–solid phase change materials with excellent anti‐leakage and form‐stable performance

AbstractPhase change materials (PCM) often encounter severe problems of leakage and shape collapse concerns. Chemical modification methods, utilizing chemical bonds to bind phase change molecular chains, have the potential to address the above‐mentioned problems radically. However, this approach often entails the use of expensive raw materials and complex processes. Therefore, a simple one‐pot preparation method had been reported using earth‐abundant and inexpensive octadecyl methacrylate (OMA) and 1,6‐hexanediol diacrylate (HD) as raw materials to prepare PCM with a molecular structure of cross‐linked polymer main chains and phase change side chains through free radical polymerization. Owing to the three‐dimensional polymer main chain structure, it exhibited excellent leakage‐proof performance, maintaining its form‐stable nature at 70°C with no obvious leakage observed during the phase change process, confirming it to be an excellent intrinsic solid–solid PCM (SSPCM). Additionally, the introduction of the cross linking segment significantly improves its thermal stability, and the 50% degradation temperature increased significantly from 228.8 to 355.9°C. Moreover, the latent heat increased with the decrease of the crosslinking density until the molar ratio of HD/OMA was reduced to 1/40 and then tended to reach constant. At the optimal ratio the latent heat of SSPCM can reach 88.23 J g−1. Excessive crosslinking density will affect the stacking tightness of molecular chains during the crystallization process, thereby reducing the latent heat.

Leveraging Electron Push-Pull Effect for Catalytic Polymerization and Degradation of a Cyclobutane Monomer System.

Ring-opening polymerization (ROP) offers a striking solution to solve problems encountered in step-growth condensation polymerization, including precise control over molecular weight, molecular weight distribution, and topology. This has inspired our interest in ROP of cycloalkanes with an ultimate goal to rethink polyolefins, which clearly poses a number of challenges. Practicality of ROP of cycloalkanes is actually limited by their low polymerizability and elusive mechanisms which arise from significantly varied ring size and non-polar C-C bonds in monomers. In this work, by using Lewis acid/Brønsted base/C(sp3)-H initiator system previously developed in our laboratory, we focus on cyclobutanes and explore the positional and electronic effects of substituents on the ring, namely electron push-pull effect, in promoting controlled polymerization to afford densely functionalized poly(cyclobutanes), as well as catalytic degradation of obtained polymers for upcycling. More importantly, experiments and DFT calculations unveil considerable population of Lewis-acid-induced thermostabilized 1,4-zwitterions, which distinguish cyclobutanes from cyclopropanes and others. All these findings would shed light on catalytic synthesis and degradation of saturated all-carbon main-chain polymers, as well as small molecule transformations of cyclobutanes.

Development, Dielectric Response, and Functionality of ZnTiO3/BaTiO3/Epoxy Resin Hybrid Nanocomposites

In the present work, hybrid nanocomposites of an epoxy resin reinforced with ZnTiO3 and BaTiO3 nanoparticles, at various filler contents, were fabricated and studied. The successful integration of ceramic nanofillers and the fine distribution of nanoparticles were confirmed via X-ray Diffraction patterns and Scanning Electron Microscopy images, respectively. Dielectric properties and related relaxation phenomena were investigated via Broadband Dielectric Spectroscopy in a wide range of frequencies and temperatures. Data analysis showed that dielectric permittivity increases with filler content, although optimum performance does not correspond to the maximum ZnTiO3 content. Four relaxation processes were observed and attributed to interfacial polarization (IP) (at low frequencies and high temperatures), glass-to-rubber transition (α-relaxation) of the epoxy matrix (at intermediate frequencies and temperatures), and local rearrangements of polar side groups of the macromolecules (β-relaxation) and small flexible groups of the main polymer chain (γ-relaxation) occurring at low temperatures and high frequencies. The ability of hybrid nanocomposites to store and retrieve energy was studied under dc conditions by employing a charging/discharging sequence. The stored and retrieved energy increases with filler content and charging voltage. The optimum ability of energy recovering, shown by the epoxy/7 phr ZnTiO3/7 phr BaTiO3 nanocomposite, ranges between 30 and 50 times more than the matrix, depending on the time instant. The employed nanoparticles induce piezoelectric properties in the nanocomposites, as found by the increase in the piezoelectric coefficient with filler content.

Cobalt-Catalyzed Cascade C-H Activation/Annulation Polymerizations toward Diversified and Multifunctional Sulfur-Containing Fused Heterocyclic Polymers.

Transition-metal-catalyzed C-H activation has greatly benefited the synthesis and development of functional polymer materials, and the construction of multifunctional fused (hetero)cyclic polymers via novel C-H activation-based polyannulations has emerged as a charming but challenging area in recent years. Herein, we report the first cobalt(III)-catalyzed cascade C-H activation/annulation polymerization (CAAP) approach that can efficiently transform readily available aryl thioamides and internal diynes into multifunctional sulfur-containing fused heterocyclic (SFH) polymers. Within merely 3 h, a series of SFH polymers bearing complex and multisubstituted S,N-doped polycyclic units are facilely and efficiently produced with high molecular weights (absolute Mn up to 220400) in excellent yields (up to 99%), which are hard to achieve by traditional methods. The intermediate-terminated SFH polymer can be used as a reactive macromonomer to controllably extend or modify polymer main chains. The structural diversity can be further enriched through facile S-oxidation and N-methylation reactions of the SFH polymers. Benefiting from the unique structures, the obtained polymers exhibit excellent solution processability, high thermal and morphological stability, efficient and readily tunable aggregate-state fluorescence, stimuli-responsive properties, and high and UV-modulatable refractive indices of up to 1.8464 at 632.8 nm. These properties allow the SFH polymers to be potentially applied in diverse fields, including metal ion detection, photodynamic killing of cancer cells, fluorescent photopatterning, and gradient-index optical materials.