Triptycene‐Based Microporous Polymer with Pending Tetrazole Moieties for CO2‐Capture Application

Triptycene‐based micorporous polymer is functionalized with CO₂‐philic tetrazole moieties via ZnCl₂‐catalyzed post‐polymerization. Gas adsorption experiments indicate that it possesses high CO₂ uptake capacity, reaching 134 cm³ g⁻¹ (26.5 wt%) at 1.0 bar and 273 K, along with high selectivity towards CO₂ over N₂ and CH₄. The porous polymeric networks present the promising potentials as efficient adsorbents in clean energy applications.

     

Planar Conjugated Polymers Containing 9,10‐Disubstituted Phenanthrene Units for Efficient Polymer Solar Cells

Four novel conjugated polymers ( P1‐4 ) with 9,10‐disubstituted phenanthrene (PhA) as the donor unit and 5,6‐bis(octyloxy)benzothiadiazole as the acceptor unit are synthesized and characterized. These polymers are of medium bandgaps (2.0 eV), low‐lying HOMO energy levels (below −5.3 eV), and high hole mobilities (in the range of 3.6 × 10⁻³ to 0.02 cm² V⁻¹ s⁻¹). Bulk heterojunction (BHJ) polymer solar cells (PSCs) with P1‐4 :PC₇₁BM blends as the active layer and an alcohol‐soluble fullerene derivative (FN‐C60) as the interfacial layer between the active layer and cathode give the best power conversion efficiency (PCE) of 4.24%, indicating that 9,10‐disubstituted PhA are potential donor materials for high‐efficiency BHJ PSCs.

     

Bifunctionalized Intrinsically Microporous Polyimides with Simultaneously Enhanced Gas Permeability and Selectivity

Two novel intrinsically microporous copolyimides synthesized by condensation reaction of 4,4′‐(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 3,3,3′,3′‐tetramethyl‐1,1′‐spirobisindane‐5,5′‐diamino‐6,6′‐diol, and 3,5‐diaminobenzoic acid with diamine ratios of 80/20 (Co‐80/20) and 50/50 (Co‐50/50) are reported. Unexpectedly, the Co‐80/20 not only demonstrates higher microporosity (300 m² g⁻¹) than the PIM‐6FDA‐OH homopolymer (190 m² g⁻¹) but also exhibits simultaneously enhanced CO₂ permeability (from 119 to 171 Barrer) and CO₂/CH₄ selectivity (from 35 to 41) after thermal annealing at 250 °C. This higher permeability originates from enhanced diffusivity (D _CO2) and the higher selectivity results from its increased diffusion selectivity (D _CO2/D _CH4). After crosslinking at 300 °C, the Co‐80/20 exhibits an even higher CO₂ permeability (261 Barrer) and almost unchanged CO₂/CH₄ selectivity.

     

Polyfluorene Polyelectrolyte Nanoparticles: Synthesis of Innovative Stabilizers for Heterophase Polymerization

Polyfluorene‐bearing bromohexyl side chains are quaternized by 1‐vinylimidazole in order to attach dialkylimidazolium bromide ionic liquid (IL) species along the conjugated backbone. Subsequently, polyfluorene polyelectrolyte nanoparticles (NPs) of 40 nm in average size are created via radical cross‐linking of the pendant vinylimidazolium groups. Anion exchange from Br⁻ to BF₄⁻, PF₆⁻, and bis(trifluoromethylsulfonyl)imide anion (TFSI⁻) renders NPs adjustable dispersability in various organic solvents. The hydrophobic‐conjugated backbone and the hydrophilic dialkylimidazolium bromide IL moieties depict an amphiphilic profile, which allows the NPs to be deployed as conductive stabilizer in the emulsion polymerization of styrene. The resultant latexes are fluorescent, tunable in size and can be transferred to organic solvents without forfeiting their colloidal stability.

     

Tandem Ring‐Opening Metathesis – Vinyl Insertion Polymerization: Fundamentals and Application to Functional Polyolefins

The accomplishments in the copolymerization of ethylene with cyclic olefins such as norborn‐2‐ene or cis‐cyclooctene via tandem ring‐opening metathesis polymerization (ROMP) – vinyl insertion polymerization (VIP) are outlined. This approach provides polyolefins with high molecular weight (600,000 < M_n < 4,500,000 g mol⁻¹) and substantial amounts of double bonds along the polymer main chain. Olefinic moieties in ROMP‐derived polymers can be converted into hydroxyl, amino, silyl, ester, or carboxylate groups by different means including controlled radical polymerization‐based grafting. The underlying concept for the switch in polymerization mechanism, the resulting pre‐catalyst requirements, limitations and challenges and the chemistry developed for functionalizing unsaturated polymers are outlined in detail.

     

A Luminescent Hypercrosslinked Conjugated Microporous Polymer for Efficient Removal and Detection of Mercury Ions

A hypercrosslinked conjugated microporous polymer (HCMP‐1) with a robustly efficient absorption and highly specific sensitivity to mercury ions (Hg²⁺) is synthesized in a one‐step Friedel–Crafts alkylation of cost‐effective 2,4,6‐trichloro‐1,3,5‐triazine and dibenzofuran in 1,2‐dichloroethane. HCMP‐1 has a moderate Brunauer–Emmett–Teller specific surface (432 m² g⁻¹), but it displays a high adsorption affinity (604 mg g⁻¹) and excellent trace efficiency for Hg²⁺. The π–π* electronic transition among the aromatic heterocyclic rings endows HCMP‐1 a strong fluorescent property and the fluorescence is obviously weakened after Hg²⁺ uptake, which makes the hypercrosslinked conjugated microporous polymer a promising fluorescent probe for Hg²⁺ detection, owning a super‐high sensitivity (detection limit 5 × 10⁻⁸ mol L⁻¹).

     

Microporous Poly(Schiff Base) Constructed from Tetraphenyladamantane Units for Adsorption of Gases and Organic Vapors

A new microporous poly(Schiff base) ( PSN‐3 ) is constructed from 1,3,5,7‐tetrakis(4‐formylphenyl)adamantane and 1,3,5,7‐tetrakis(4‐aminophenyl)adamantane through an A₄‐A₄′ reaction. The surface and internal morphologies of porous PSN‐3 are examined by FE‐SEM and HR‐TEM. PSN‐3 exhibits a BET surface area of 865 m² g⁻¹ with a major pore size around 0.6 nm. Moreover, PSN‐3 can uptake 1.32 wt% H₂ (77 K/1 bar), 13.6 wt% CO₂ (273 K/1 bar), 80.5 wt% benzene, and 63.7 wt% cyclohexane (298 K/0.9 bar). The adsorption selectivities for CO₂/N₂, CO₂/CH₄, benzene/N₂, and benzene/H₂O are 88, 16, 267, and 19, respectively. The high adsorption capacities and selectivities for gases and vapors make PSN‐3 a promising candidate for H₂ storage, CO₂ capture, and recovery of organic pollutants.

     

Ugi Reactions with CO2: Access to Functionalized Polyurethanes,Polycarbonates, Polyamides,and Polyhydantoins

A novel strategy for the incorporation of carbon dioxide into polymers is introduced. For this purpose, the Ugi five‐component condensation (Ugi‐5CC) of an alcohol, CO₂, an amine, an aldehyde, and an isocyanide is used to obtain step‐growth monomers. Polymerization via thiol‐ene reaction or polycondensation with diphenyl carbonate gives diversely substituted polyurethanes or alternating polyurethane‐polycarbonates, respectively. Furthermore, the application of 1,12‐diaminododecane and 1,6‐diisocyanohexane as bifunctional components in the Ugi‐5CC directly results in the corresponding polyamide bearing methyl carbamate side chains ( = 19 850 g mol⁻¹). The latter polymer is further converted into the corresponding polyhydantoin in a highly straightforward fashion.

     

Carbon Dioxide‐Controlled Assembly of Water‐Soluble Conjugated Polymers Catalyzed by Carbonic Anhydrase

The CO₂‐responsive and biocatalytic assembly based on conjugated polymers has been demonstrated by combining the signal amplification property of the polythiophene derivative (PTP) and the catalytic actions of carbonic anhydrase (CA). CO₂ is applied as a new trigger mode to construct the smart assembly by controlling the electrostatic and hydrophobic interactions between the PTP molecules in aqueous solution, leading to the visible fluorescence changes. Importantly, the assembly transformation of PTP can be specifically and highly accelerated by CA based on the efficient catalytic activity of CA for the inter‐conversion between CO₂ and HCO₃⁻, mimicking the CO₂‐associated biological processes that occurred naturally in living organisms. Moreover, the PTP‐based assembly can be applied for biomimetic CO₂ sequestration with fluorescence monitoring in the presence of CA and calcium.

     

Novel Donor–Acceptor Polymer Containing 4,7‐Bis(thiophen‐2‐yl)benzo[c][1,2,5]thiadiazole for Polymer Solar Cells with Power Conversion Efficiency of 6.21%

In order to improve the solution processability of 4,7‐bis(thiophen‐2‐yl)benzo[c][1,2,5]thiadiazole (DTBT)‐based polymers, novel donor–acceptor polymer PTOBDTDTBT containing DTBT and benzo[1,2‐b:4,5‐b′]dithiophene (BDT) with conjugated side chain is designed and synthesized with narrow band gap 1.67 eV and low lying HOMO energy level −5.4 eV. The blend film of PTOBDTDTBT and PC₇₁BM exhibits uniform and smooth film with root‐mean‐square (RMS) surface roughness 1.15 nm because of the excellent solubility of PTOBDTDTBT when six octyloxy side chains are introduced. The hole mobility of the blend film is measured to be 4.4 × 10⁻⁵ cm² V⁻¹s⁻¹ by the space‐charge‐limited current (SCLC) model. The optimized polymer solar cells (PSCs) based on PTOBDTDTBT /PC₇₁BM exhibits an improved PCE of 6.21% with V_oc = 0.80 V, J_sc = 11.94 mA cm⁻² and FF = 65.10%, one of the highest PCE in DTBT containing polymers.

     

Propargyl‐Functional Aliphatic Polycarbonate Obtained from Carbon Dioxide and Glycidyl Propargyl Ether

The synthesis of propargyl‐functional poly(carbonate)s with different content of glycidyl propargyl ether (GPE) units is achieved via the copolymerization of propargyl glycidyl ether and carbon dioxide. A new type of functional poly(carbonate) synthesized directly from CO₂ and the glycidyl ether is obtained. The resulting polymers show moderate polydispersities in the range of 1.6–2.5 and molecular weights in the range of 7000–10 500 g mol⁻¹. The synthesized copolymers with varying number of alkyne functionalities and benzyl azide are used for the copper‐catalyzed Huisgen‐1,3‐dipolar addition. Moreover, the presence of vicinal alkyne groups opens a general pathway to produce functional aliphatic poly(carbonate)s from a single polymer scaffold.

     

Shape‐Memory PVDF Exhibiting Switchable Piezoelectricity

In this study, a material is designed which combines the properties of shape‐memory and electroactive polymers. This is achieved by covalent cross‐linking of polyvinylidene fluoride. The resulting polymer network exhibits excellent shape‐memory properties with a storable strain of 200%, and fixity as well as recovery values of 100%. Programming upon rolling induces the transformation from the nonelectroactive α‐phase to the piezoelectric β‐phase. The highest β‐phase content is found to be 83% for a programming strain of 200% affording a d₃₃ value of −30 pm V⁻¹. This is in good accordance with literature known values for piezoelectric properties. Thermal triggering this material does not only result in a shape change but also renders the material nonelectroactive.

     

Single‐Chain Self‐Folding of Synthetic Polymers Induced by Metal–Ligand Complexation

The controlled folding of a single polymer chain is for the first time realized by metal‐ complexation. α,ω‐Bromine functional linear polymers are prepared via activators regenerated by electron transfer (ARGET) ATRP (_,SEC = 5900 g mol⁻¹, Đ = 1.07 and 12 000 g mol⁻¹, Đ = 1.06) and the end groups of the polymers are subsequently converted to azide functionalities. A copper‐catalyzed azide–alkyne cycloaddition (CuAAC) reaction is carried out in the presence of a novel triphenylphosphine ligand and the polymers to afford homotelechelic bis‐triphenylphosphine polymeric‐macroligands (MLs) (_,SEC = 6600 g mol⁻¹, Đ = 1.07, and 12 800 g mol⁻¹, Đ = 1.06). Single‐chain metal complexes (SCMCs) are formed in the presence of Pd(II) ions in highly diluted solution at ambient temperature. The results derived via ¹H and ³¹P{¹H} NMR experiments, SEC, and DLS unambiguously evidence the efficient formation of SCMCs via metal ligand complexation.

     

Synthesis of High Molecular Weight Cyclic Poly(ε‐caprolactone)s of Variable Ring Size Based on a Light‐Induced Ring‐Closure Approach

High molecular weight cyclic poly(ε‐caprolactone)s (cPCLs) with variable ring size are synthesized via light‐induced ring closure of α,ω‐anthracene‐terminated PCL (An‐PCL‐An). The ring size of cPCL is tunable simply by adjusting the polymer concentration from 10 to 100 mg mL⁻¹ in THF. The cyclo­addition via the bimolecular cyclization of An‐PC‐An is well characterized by a variety of analyses such as ¹H NMR and UV–vis spectroscopies, gel‐permeation chromatography, and differential scanning calorimetry. The reversible dimerization of An induced by heating enables the cyclic PCL to have a switchable “on–off” capability. This novel light‐induced ring‐closure technique can be one of the most powerful candidates for producing various well‐defined cyclic polymers in highly concentrated polymer solution.

     

Highly Sensitive Dual‐Mode Fluorescence Detection of Lead Ion in Water Using Aggregation‐Induced Emissive Polymers

A series of fluorene‐based conjugated polymers containing the aggregation‐induced emissive (AIE)‐active tetraphenylethene and dicarboxylate pseudocrown as a receptor exhibits a unique dual‐mode sensing ability for selective detection of lead ion in water. Fluorescence turn‐off and turn‐on detections are realized in 80%–90% and 20% water in tetrahydrofuran (THF), respectively, for lead ion with a concentration as low as 10⁻⁸ m .

     

Light‐Induced Disintegration of Robust Physically Cross‐Linked Polymer Networks

Photodegradable physically cross‐linked polymer networks are prepared from self‐assembly of photolabile triblock copolymers. Linear triblock copolymers composed of poly (o‐nitrobenzyl methacrylate) and poly(ethylene glycol) (PEG) segments of variable molecular weights were synthesized using atom transfer radical polymerization. Triblock polymers with low‐molecular‐weight PEG segments form solid films upon hydration with robust mechanical properties including a Young's modulus of 76 ± 12 MPa and a toughness of 108 ± 31 kJ m⁻³. Triblock polymers with high‐molecular‐weight PEG segments form physically cross‐linked hydrogels at room temperature with a dynamic storage modulus of 13 ± 0.6 kPa and long‐term stability in hydrated environments. Both networks undergo photodegradation upon irradiation with long wave UV light.

     

Copolymerization of Epichlorohydrin and CO2 Using Zinc Glutarate: An Additional Application of ZnGA in Polycarbonate Synthesis

The use of zinc glutarate (ZnGA) as a heterogeneous catalyst for the copolymerization of epichlorohydrin, an epoxide with an electron‐withdrawing substituent, and CO₂ is reported. This catalyst shows the highest selectivity (98%) for polycarbonate over the cyclic carbonate in epichlorohydrin/CO₂ copolymerization under mild conditions. The (epichlorohydrin‐co‐CO₂) polymer exhibits a high glass transition temperature (T_g), 44 °C, which is the maximum T_g value obtained for the (epichlorohydrin‐co‐CO₂) polymer to date.

     

Alkylphenyl Substituted Naphthodithiophene: A New Building Unit with Conjugated Side Chains for Semiconducting Materials

In this article, a versatile 2‐D conjugated polymer, PNDTP‐DPP, containing alkylphenyl substituted naphthodithiophene is synthesized and characterized. PNDTP‐DPP exhibits good solubility and crystallinity with a π−π stacking distance of ≈3.7 Å. Investigation of polymer solar cells (PSCs) and organic field‐effect transistors (OFET) demonstrates a promising power conversion efficiency (PCE) of 4.11% and a high hole mobility of up to 0.86 cm² V^–1 s^–1, so this is one of the few examples of versatile polymers that show both good field‐effect mobility and PCE.

     

Optically Active Conjugated Polymer from Solvent Chirality Transfer Polymerization in Monoterpenes

Disubstituted acetylene monomers [1,2‐diphenylacetylenes (DPAs: DPA‐pC1, DPA‐mC1, DPA‐pC8); 1‐phenyl‐2‐hexylacetylene (PHA‐pC1)] are tested for asymmetric polymerization in chiral monoterpenes used as solvents and compared with the corresponding monosubstituted acetylene monomer [1‐phenylacetylene (PA‐pC1)]. DPA‐pC1 containing a trimethylsilyl group in the para‐position of the phenyl ring produces an optically active polymer with a large Cotton effect, despite the absence of a stereogenic center. The polymer sample obtained by polymerization in 87% ee (–)‐α‐pinene shows the strongest CD signal (g_CD value at 385 nm: ∼3.2 × 10⁻³). The Cotton bands of the polymers obtained in (–)‐ and (+)‐α‐pinenes show the opposite sign in the CD signals. Theoretical calculations show that only the cis‐cisoid model adopts a helical conformation. A time‐correlated single photon counting experiment shows that the emission of the chiral polymer originates from a virtually single excited species with a 98% component fraction. This polymer solution does not show any significant decrease in g_CD value over a wide temperature range of 20 to 80 °C. No noticeable decrease in the g_CD value is detected when the polymer solution is kept at relatively low temperatures for a prolonged period (35 d). In contrast, the other polymers show no CD signal.

     

Balanced Ambipolar Poly(diketopyrrolopyrrole‐alt‐tetrafluorobenzene) Semiconducting Polymers Synthesized via Direct Arylation Polymerization

The synthesis of an ambipolar π‐conjugated copolymer consisting of alternating diketopyrrolopyrrole and tetrafluorobenzene via direct arylation polymerization (DAP) is reported. Two different combinations of monomers are investigated under various catalytic conditions for DAP. The target polymer obtained under an optimized catalytic condition shows minimal structural defects, a number‐average molecular weight of 33.2 kDa, and balanced electron and hole mobility of 1 × 10⁻² cm² V⁻¹ S⁻¹ in the organic field‐effect transistors fabricated and tested under ambient conditions.