Analysis of diverse direct arylation polymerization (DArP) conditions toward the efficient synthesis of polymers converging with stille polymers in organic solar cells

Despite the emergence of direct arylation polymerization (DArP) as an alternative method to traditional cross‐coupling routes like Stille polymerization, the exploration of DArP polymers in practical applications like polymer solar cells (PSCs) is limited. DArP polymers tend to have a reputation for being marginally inferior to Stille counterparts due to the increased presence of defects that result from unwanted side reactions in direct arylation, such as unselective C‐H bond activation and homocoupling. We report ten DArP protocols across the three major classes of DArP to generate poly[(2,5‐bis(2‐hexyldecyloxy)phenylene)‐alt‐(4,7‐di(thiophen‐2‐yl)benzo[c][1,2,5]thiadiazole)] (PPDTBT). Through evaluation of the method and resulting photophysical and electronic properties, we show not all DArP methods are suitable for generating device‐quality alternating copolymers. When DArP PPDTBT was synthesized in superheated THF with Cs₂CO₃, neodecanoic acid, and P(o‐anisyl)₃, it generated polymers of exceptional quality that performed comparably to Stille counterparts in both roll coated ITO‐free and spin‐coated ITO devices. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2907–2918     

Minimization of the auxiliary reagent loading for direct arylation polymerization (DArP) of 2‐bromo‐3‐hexylthiophene

In this work, we present a powerful set of synthetic strategies aimed at minimization of auxiliary reagent loading for direct arylation polymerization (DArP) of 2‐bromo‐3‐hexylthiophene. As such, we report efficient lowering of Pd(OAc)₂ catalyst loading as well as loading of other auxiliary reagents, such as neodecanoic acid and N,N‐dimethylacetamide. Unprecedented low loadings of catalyst down to 0.0313% (313 ppm) were achieved, while producing polymer in high yield (91% after Soxhlet extraction), with a high molecular weight (24.2 kDa) and carefully controlled chemical structure thus making the optimized DArP protocol significantly more cost‐effective, convenient, sustainable, and environmentally friendly. The resulting polymer samples were thoroughly investigated in terms of their chemical structure as well as optical, thermal, chain ordering and electronic properties using GPC analysis, ¹H NMR, MALDI, UV–vis, GIXRD spectroscopy, DSC, and SCLC hole mobility measurements. The results demonstrate that the reagent lowering strategies increase the polymer regioregularity from 94.6 to 96.5% as evidenced by ¹H NMR spectra and corroborated by GIXRD, DSC, and UV–vis measurements. Additionally, polymer samples obtained at low reagent loading are more uniformly proton‐terminated as evidenced by ¹H NMR and MALDI end‐group analysis. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1492–1499     

The effect of amide solvent structure on the direct arylation polymerization (DArP) of 2‐Bromo‐3‐hexylthiophene

In this work, we investigate the influence of the amide solvent chemical structure on the properties of poly(3‐hexylthiophene) (P3HT) prepared via direct arylation polymerization (DArP). Our findings indicate that for successful polymerization the amide must possess an acyclic aliphatic structure since cyclization of an amide results in a complete shutdown of DArP reactivity as evidenced by failed polymerization in N‐methylpyrrolidone, whereas the presence of an aromatic motif renders the amide solvent susceptible to C? H activation and leads to incorporation of the solvent structure into the P3HT backbone, as demonstrated on the example of N,N‐diethylbenzamide. Additionally, we observed that the steric bulk of alkyl substituents on both the nitrogen atom and the carbonyl group within the amide structure has to be delicately balanced for optimal DArP reactivity. In the optimal cases, P3HT is obtained in high yield, with high molecular weight and contains a minimal amount of structural defects. The obtained polymer samples were comprehensively studied in terms of their chemical structure, optical, thermal and solid‐state properties in thin films using GPC analysis, ¹H NMR, MALDI, UV–vis, GIXRD spectroscopy, and DSC. We additionally note a drastic difference of the amide solvent effect between DArP and Stille polymerization. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2494–2500     

Preparation of semi‐alternating conjugated polymers using direct arylation polymerization (DArP) and improvement of photovoltaic device performance through structural variation

The results herein expand on optimized direct arylation polymerization (DArP) conditions for defect‐free poly[(2,5‐bis (2‐hexyldecyloxy)phenylene)‐alt‐(4,7‐di(thiophen‐2‐yl)benzo[c][1,2,5] thiadiazole)] (PPDTBT). Semi‐alternating and alternating donor–acceptor polymers containing alkoxy phenylene, dithienyl‐substituted thieno[3,4‐c]pyrrole‐4,6‐dione (DTTPD), and dithienyl‐substituted diketopyrrolopyrrole (DTDPP) were prepared via DArP, including a four‐component semi‐alternating copolymer PPDTDPPTPD. Variation of the alkoxy substituents on the phenylene donor including n‐hexyl, 2‐ethylhexyl, or 2‐hexyldecyl allowed for the tuning of thephysical and electronic properties. Molecular weights (M _n) ranged from 3.07 to 28.3 kDa for the PPDTTPD polymers and 2.63‐44.0 kDa for the PPDTDPP polymers, depending on the alkoxy substituents. Absorbance maxima and HOMO energies were varied from 550 to 602 nm and ?5.31 to ?5.69 eV for the PPDTTPD polymers and from 671 to 794 nm and ?5.41 to ?5.55 eV for the PPDTDPP polymers, respectively. Additive‐free, bulk heterojunction (BHJ) solar cells were fabricated, and the fill‐factors obtained (0.57–0.63) are some of the highest reported for polymers prepared using DArP. Higher molecular weight polymers for both PPDTTPD (28 kDa) and PPDTDPP (44 kDa) series performed poorly in solar cells. In contrast, the semi‐alternating polymers of lower M _n for the PPDTTPD (12.4 kDa) and PPDTDPP (9.05 kDa) series, incorporating both n‐hexyl and 2‐hexyldecyl alkoxy phenylene donors, provided power conversion efficiencies (PCE) of 3.26% and 3.49%, respectively. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3370–3380     

Coordination polymers based on building blocks of dimethyltin(IV) Chloride iso‐thiocyanate and dimethyltin(IV) di‐iso‐thiocyanate with pyrazine‐2‐carboxylate and 4, 4′‐bipyridine

The reaction of 4,4′‐bipy with dimethyltin(IV) chloride iso‐thiocyanate affords the one‐dimensional (1D) coordination polymer, [Me₂Sn(NCS)Cl·(4,4′‐bipy)]_n ( 1 ), whereas reaction of dimethyltin(IV) dichloride with sodium pyrazine‐2‐carboxylate in the presence of potassium iso‐thiocyanate affords the two‐dimensional (2D) coordination polymer, {[Me₂Sn(C₄H₃N₂COO)₂]₂ [Me₂Sn(NCS)₂]}_n ( 2 ). Both coordination polymers were characterized by elemental analysis and infrared spectroscopy in addition to ¹H and ¹³C NMR spectroscopy of the soluble coordination polymer ( 1 ). A single‐crystal structure determination showed that the asymmetric unit in 1 contains Me₂Sn(NCS)Cl and 4,4′‐bipy moieties and a 1D infinite rigid chain structure forms through bridging of the 4,4′‐bipy ligand between tin atoms and the geometry around the tin atom is a distorted octahedral. Coordination polymer 2 contains two distinct tin atom geometrics in which one tin atom is seven coordinate, and the other is six coordinate. The two tin atom environments are best described as a pentagonal bipyramidal in the former and distorted octahedral in the latter where the carboxylate groups bridge the two tin atoms and construct a 2D‐coordination polymer. The ¹¹⁹Sn NMR spectroscopy indicates the octahedral geometry of 1 retains in solution. © 2011 Wiley Periodicals, Inc. Heteroatom Chem 22:699–706, 2011; View this article online at wileyonlinelibrary.com . DOI 10.1002/.20736     

Bulk polymerization of p‐dioxanone using a cyclic tin alkoxide as initiator

Poly(p‐dioxanone) with an inherent viscosity of over 1 dL/g has been synthesized using the cyclic tin alkoxide 1‐di‐n‐butyl‐1‐stanna‐2,5‐dioxacyclopentane as initiator. Poly(p‐dioxanone) was synthesized in bulk and the results have been compared with polymerizations using tin (II) 2‐ethylhexanoate (Sn(Oct)₂) as catalyst. Sn(Oct)₂ has often been reported to be an effective catalyst for the synthesis of poly(p‐dioxanone), but here it is compared with an initiator which is less prone to catalyze transesterification reactions. The results demonstrate that the cyclic tin initiator is a promising alternative for the synthesis of poly(p‐dioxanone) with a high inherent viscosity. Poly(p‐dioxanone) is a polymer with mechanical properties and a degradation rate suitable for tissue engineering applications. Both the cyclic tin initiator and Sn(Oct)₂ gave, under some reaction conditions, inherent viscosities around 1 dL/g. The best polymer synthesized using the cyclic tin initiator had a strain‐at‐break of 515% and a stress‐at‐break of 43 MPa. The inherent viscosity of this polymer was 1.16 dL/g, while Sn(Oct)₂ resulted in a polymer with an inherent viscosity less than 0.4 dL/g under the same reaction conditions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5552–5558, 2007     

Direct arylation polymerization toward a narrow bandgap donor–acceptor conjugated polymer of alternating 5,6‐difluoro‐2,1,3‐benzothiadiazole and alkyl‐quarternarythiophene: From synthesis,optoelectronic properties to devices

ABSTRACT: Direct arylation polymerization (DAP) enabled facile synthesis of a narrow bandgap donor–acceptor conjugated polymer (PDFBT‐Th₄) composed of alternating 5,6‐difluoro‐2,1,3‐benzothiadiazole and alkyl‐quaternarythiophene. The optimized reaction condition of DAP catalyzed with Pd(OAc)₂/(o‐MeOPh)₃P/PivOH/K₂CO₃ in o‐xylene led to the target polymer with a number‐average molecular weight (M_n) of 14.6 kDa without noticeable homocoupling or β‐branching defects. UV‐vis absorption spectra of PDFBT‐Th₄ indicate strong interchain aggregation in films. While the C‐H selectivity and the alternating polymer structure of PDFBT‐Th₄ synthesized via DAP are comparable to those of the same type polymers synthesized via Stille coupling, the batch of PDFBT‐Th₄ synthesized via optimal DAP, despite its lower M_n, showed higher hole mobility in field effect transistors and larger power conversion efficiency in organic solar cell devices. These results further demonstrate the promising potential of DAP for efficient synthesis of high‐performance D‐A conjugated polymers for broad optoelectronic applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1869–1879     

Novel high‐performance polymer memory devices containing (OMe)2tetraphenyl‐p‐phenylenediamine moieties

The functional polyimide (OMe)₂TPPA‐6FPI ( PI ) and the polyamide (OMe)₂TPPA‐6FPA ( PA ) consisting of electron‐donating N,N′‐bis(4‐aminophenyl)‐N,N′‐di(4‐methoxylphenyl)1,4‐phenylenediamine [(OMe)₂TPPA‐diamine] for memory application were prepared in this study. These polyimide and polyamide memory devices were fabricated with the sandwich configuration of indium tin oxide (ITO)/polymer/Al, and could be switched from the initial low‐conductivity (OFF) state to the high‐conductivity (ON) state with high ON/OFF current ratios of 10⁷ and 10⁹, respectively. PI exhibited dynamic random access memory (DRAM) performance, whereas PA showed static random access memory (SRAM) behavior. To get more insight into the memory behaviors of these two different types of polymer memory devices, molecular simulation on the basic unit was carried out. Furthermore, the differences of highest occupied molecular orbital (HOMO) energy level, lowest unoccupied molecular orbital (LUMO) charge density isosurfaces, dipole moment, and linkage conformation between PI and PA were found to affect the volatile memory behavior. Both polymer memory devices revealed excellent stability with long operation time of 10⁴ s at continuous applied voltage of ‐2 V. The effect of polymer thickness on the volatile memory behavior of PA was also investigated in this study. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

A comparative study of fluorine substituents for enhanced stability of flexible and ITO‐free high‐performance polymer solar cells

Two low‐band gap polymer series based on benzo[1,2‐b:4,5‐b′]dithiophene (BDT) and dithienylbenzothiadiazole, with different numbers of fluorine substituents on the 2,3,1‐benzothiadiazole unit, have been synthesized and explored in a comparative study of the photochemical stability and operational lifetime in flexible large area roll‐coated bulk heterojunction solar cells. The two polymer series have different side chains on the BDT unit, namely 2‐hexyldecyloxy (BDT_HDO) ( P1–P3 ) or 2‐hexyldecylthiophene (BDT_THD) ( P4–P6 ). The photochemical stability clearly shows that the stability enhances along with the number of fluorine atoms incorporated on the polymer backbone. Fabrication of the polymer solar cells based on the materials was carried out in ambient atmosphere on a roll coating/printing machine employing flexible and indium‐tin‐oxide‐free plastic substrates. Solar cells based on the P4–P6 series showed the best performance, reaching efficiencies up to 3.8% for an active area of 1 cm², due to an enhanced current compared to P1–P3 . Lifetime measurements, carried out according to international summit on OPV stability (ISOS), of encapsulated devices reveals an initial fast decay for P1–P6 in the performance followed by a much slower decay rate, still retaining 40–55% of their initial performance after 250 h of testing under ISOS‐L‐1 conditions. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 893–899     

Significant Difference in Semiconducting Properties of Isomeric All‐Acceptor Polymers Synthesized via Direct Arylation Polycondensation

The direct arylation polycondensation (DArP) appeared as an efficient method for producing semiconducting polymers but often requires acceptor monomers with orienting or activating groups for the reactive carbon‐hydrogen (C‐H) bonds, which limits the choice of acceptor units. In this study, we describe a DArP for producing high‐molecular‐weight all‐acceptor polymers composed of the acceptor monomers without any orienting or activating groups via a modified method using Pd/Cu co‐catalysts. We thus obtained two isomeric all‐acceptor polymers, P1 and P2, which have the same backbone and side‐chains but different positions of the nitrogen atoms in the thiazole units. This subtle change significantly influences their optoelectronic, molecular packing, and charge‐transport properties. P2 with a greater backbone torsion has favorable edge‐on orientations and a high electron mobility μ_e of 2.55 cm² V^?1 s^?1. Moreover, P2‐based transistors show an excellent shelf‐storage stability in air even after the storage for 1 month.     

Thienoisoindigo‐based small molecules and narrow bandgap polymers synthesized via C–H direct arylation coupling

Thienoisoindigo (TIIG) has emerged as an attractive building block for high‐performance organic optoelectronic devices. Here we report the first synthesis of a series of π‐conjugated TIIG‐based small molecules and alternating copolymers via direct C–H arylation, which enables the efficient synthesis without use of flammable and toxic orgametallic reagents in fewer steps compared Suzuki and Stille coupling. The direct arylation coupling between TIIG and two respective mono‐bromo aryl reactants clearly shows that the α‐H is more reactive than the β‐H in the thiophene unit of TIIG. The high regioselectivity of TIIG monomer warrants the successful synthesis of high‐quality alternating copolymers with minimal structural defects. PTIIG‐BT polymer synthesized via direct arylation polymerization (DAP) showed comparable molecular weight and hole mobility than the same polymer previously synthesized via Suzuki coupling. Moreover, the two new polymers (PTIIG‐TF and PTIIG‐2FBT) synthesized via DAP showed hole mobility up to 10^?3 cm² V^?1 s^?1 in FET devices fabricated and tested under ambient conditions. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2015–2031     

Synthesis of α‐Aryl Esters and Nitriles: Deaminative Coupling of α‐Aminoesters and α‐Aminoacetonitriles with Arylboronic Acids

Transition‐metal‐free synthesis of α‐aryl esters and nitriles using arylboronic acids with α‐aminoesters and α‐aminoacetonitriles, respectively, as the starting materials has been developed. The reaction represents a rare case of converting C(sp³)? N bonds into C(sp³)? C(sp²) bonds. The reaction conditions are mild, demonstrate good functional‐group tolerance, and can be scaled up.     

Continuous process for the production of vinyl acetate‐ethylene emulsion copolymers

A lab‐scale experimental program was conducted to determine the feasibility of producing vinyl acetate‐ethylene (VAE) emulsion copolymers via a continuous reaction process, using poly(vinyl alcohol), or PVOH, as a protective colloid. A process configuration of multiple stirred‐tanks in series was utilized. Comparisons were made between continuous and batch processes with regard to final‐product properties. As expected, notable differences in the breadths of the particle‐size distributions obtained via the two processes were observed. However, these differences did not appreciably alter product performance in tile‐mortar applications (as measured by plywood‐to‐quarry‐tile adhesive strengths). Additionally, for the continuous process, in‐process and final‐product samples were compared to determine how polymer properties varied with conversion.     

Optimization of direct arylation polymerization conditions for the synthesis of poly(3‐hexylthiophene)

Direct arylation polymerization (DArP) is an emerging alternative to Stille and Suzuki polymerizations. This method is attractive as it allows preparation of high‐molecular‐weight conjugated polymers in good yield without the need to metallate monomers. Despite this promise, for poly(3‐hexylthiophene) (P3HT) and related polymers that have β‐protons on the thiophene ring, DArP is known to produce β‐defects, which make the polymer properties different from polymers produced by traditional methods. Here, we demonstrate that DArP conditions based on simple, inexpensive, and bench‐stable reagents can be tuned to limit the amount of defects and produce P3HT with properties remarkably similar to Stille P3HT. Specifically, lowering the reaction temperature, lowering the amount of catalyst, and using a bulkier carboxylate ligand is critical. Optimized conditions include reacting 2‐bromo‐3‐hexylthiophene with 0.25 mol % of Pd(OAc)₂, 1.5 equivalents of K₂CO₃, and 0.3 equivalents of neodecanoic acid in N,N‐dimethylacetamide at 70 °C and give DArP P3HT with ～60% yield, regioregularity of 93.5%, molecular weight of 20 kDa, polydispersity of 2.8, and melting point of 217 °C, providing a very close match to Stille P3HT, which is obtained with 70–80% yield, 91–94% regioregularity, molecular weight of 15–25 kDa, polydispersity of 2.5–2.8, and melting point of 214–221 °C. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2660–2668     

Hexagonal‐Shaped Tin Glycolate Particles: A Preliminary Study of Their Suitability as Li‐Ion Insertion Electrodes

Tin glycolate particles were prepared by a simple, one‐step, polyol‐mediated synthesis in air in which tin oxalate precursor was added to ethylene glycol and heated at reflux. Hexagonal‐shaped, micron‐sized tin glycolate particles were formed when the solution had cooled. A series of tin oxides was produced by calcination of the synthesized tin glycolate at 600–800 °C. It was revealed that the micron‐sized, hexagonal‐shaped tin glycolate now consisted of nanosized tin‐based particles (80–120 nm), encapsulated within a tin glycolate shell. XRD, TGA, and FT‐IR measurements were conducted to account for the three‐dimensional growth of the tin glycolate particles. When applied as an anode material for Li‐ion batteries, the synthesized tin glycolate particles showed good electrochemical reactivity in Li‐ion insertion/deinsertion, retaining a specific capacity of 416 mAh g^?1 beyond 50 cycles. This performance was significantly better than those of all the other tin oxides nanoparticles (<160 mAh g^?1) obtained after heat treatment in air. We strongly believe that the buffering of the volume expansion by the glycolate upon Li–Sn alloying is the main factor for the improved cycling of the electrode.     

Organocatalyzed Photo‐Atom Transfer Radical Polymerization of Methacrylic Acid in Continuous Flow and Surface Grafting

The organocatalyzed photo‐atom transfer radical polymerization (photoATRP) using 10‐phenylphenothiazine as catalyst is studied toward its use in methacrylic acid (MAA) polymerization and surface grafting. The organocatalyzed photoATRP of methyl methacrylate (MMA) is first optimized for continuous flow synthesis in order to assess the livingness of the polymerization. MMA can be polymerized in batch and in flow; however, conversions are limited by the loss of bromine functionality and hence high conversions have to be traded in with increasing dispersities. Also, MAA is polymerized successfully in continuous flow with similar limitations. Flow conditions are transferred to surface grafting from silanized silicon wafers. The presence of ATRP initiators after silanization is confirmed by secondary ion mass spectrometry and X‐ray photoelectron spectroscopy. Dense polymethacrylic acid brush films are successfully produced, which is not directly accessible via classical copper‐mediated ATRP techniques.     

Tunable Self‐Assembly of Triazole‐Linked Porphyrin–Polymer Conjugates

The convergence of supramolecular chemistry and polymer science offers many powerful approaches for building functional nanostructures with well‐defined dynamic behaviour. Herein we report the efficient “click” synthesis and self‐assembly of AB₂‐ and AB₄‐type multitopic porphyrin–polymer conjugates (PPCs). PPCs were prepared using the copper(I)‐catalysed azide–alkyne cycloaddition (CuAAC) reaction, and consisted of linear polystyrene, poly(butyl acrylate), or poly(tert‐butyl acrylate) arms attached to a zinc(II) porphyrin core via triazole linkages. We exploit the presence of the triazole groups obtained from CuAAC coupling to direct the self‐assembly of the PPCs into short oligomers (2–6 units in length) via intermolecular porphyrinatozinc–triazole coordination. By altering the length and grafting density of the polymer arms, we demonstrate that the association constant of the porphyrinatozinc–triazole complex can be systematically tuned over two orders of magnitude. Self‐assembly of the PPCs also resulted in a 6 K increase in the glass transition temperature of the bulk material compared to a non‐assembling PPC. The modular synthesis and tunable self‐assembly of the triazole‐linked PPCs thus represents a powerful supramolecular platform for building functional nanostructured materials.     

Hole‐transporting host‐polymer series consisting of triphenylamine basic structures for phosphorescent polymer light‐emitting diodes

A series of novel styrene derived monomers with triphenylamine‐based units, and their polymers have been synthesized and compared with the well‐known structure of polymer of N,N′‐bis(3‐methylphenyl)‐N,N′‐diphenylbenzidine with respect to their hole‐transporting behavior in phosphorescent polymer light‐emitting diodes (PLEDs). A vinyltriphenylamine structure was selected as a basic unit, functionalized at the para positions with the following side groups: diphenylamine, 3‐methylphenyl‐aniline, 1‐ and 2‐naphthylamine, carbazole, and phenothiazine. The polymers are used in PLEDs as host polymers for blend systems with the following device configuration: glass/indium–tin–oxide/PEDOT:PSS/polymer‐blend/CsF/Ca/Ag. In addition to the hole‐transporting host polymer, the polymer blend includes a phosphorescent dopant [Ir(Me‐ppy)₃] and an electron‐transporting molecule (2‐(4‐biphenyl)‐5‐(4‐tert‐butylphenyl)‐1,3,4‐oxadiazole). We demonstrate that two polymers are excellent hole‐transporting matrix materials for these blend systems because of their good overall electroluminescent performances and their comparatively high glass transition temperatures. For the carbazole‐substituted polymer (T_g = 246 °C), a luminous efficiency of 35 cd A^?1 and a brightness of 6700 cd m^?2 at 10 V is accessible. The phenothiazine‐functionalized polymer (T_g = 220 °C) shows nearly the same outstanding PLED behavior. Hence, both these polymers outperform the well‐known polymer of N,N′‐bis(3‐methylphenyl)‐N,N′‐diphenylbenzidine, showing only a luminous efficiency of 7.9 cd A^?1 and a brightness of 2500 cd m^?2 (10 V). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3417–3430, 2010     

Cost‐Effective,High‐Performance Porous‐Organic‐Polymer Conductors Functionalized with Sulfonic Acid Groups by Direct Postsynthetic Substitution

We demonstrate the facile microwave‐assisted synthesis of a porous organic framework 1 and the sulfonated solid ( 1S ) through postsubstitution. Remarkably, the conductivity of 1S showed an approximately 300‐fold enhancement at 30 °C as compared to that of 1 , and reached 7.72×10⁻² S cm⁻¹ at 80 °C and 90 % relative humidity. The superprotonic conductivity exceeds that observed for any conductive porous organic polymer reported to date. This material, which is cost‐effective and scalable for mass production, also revealed long‐term performance over more than 3 months without conductivity decay.     

Cost‐Effective,High‐Performance Porous‐Organic‐Polymer Conductors Functionalized with Sulfonic Acid Groups by Direct Postsynthetic Substitution

We demonstrate the facile microwave‐assisted synthesis of a porous organic framework 1 and the sulfonated solid ( 1S ) through postsubstitution. Remarkably, the conductivity of 1S showed an approximately 300‐fold enhancement at 30 °C as compared to that of 1 , and reached 7.72×10^?2 S cm^?1 at 80 °C and 90 % relative humidity. The superprotonic conductivity exceeds that observed for any conductive porous organic polymer reported to date. This material, which is cost‐effective and scalable for mass production, also revealed long‐term performance over more than 3 months without conductivity decay.