Synthesis and optoelectronic properties of novel benzodifuran semiconducting polymers

Two new semiconducting polymers poly{4,8‐bis(4‐decylphenylethynyl)benzo[1,2‐b:4,5‐b′]difuran} ( P1 ) and poly {4,8‐bis(4‐decylphenylethynyl)benzo[1,2‐b:4,5‐b′]difuran‐alt‐4,8‐bis(4‐decylphenylethynyl)benzo[1,2‐b:4,5‐b′]dithiophene} ( P2 ) have been synthesized. These polymers were tested in bulk heterojunction solar cells yielding power conversion efficiencies of 1.19% for P1 and 0.79% for P2 . The surface morphology of the solar cell devices indicated that both the polymers display a granular morphology with smoother films displaying higher power conversion efficiencies. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Crystallographic characterization of the first reported crystalline form of the potent hallucinogen (R)‐2‐amino‐1‐(8‐bromobenzo[1,2‐b;5,4‐b′]difuran‐4‐yl)propane or `bromodragonfly': the 1:1 anhydrous proton‐transfer compound with 3,5‐dinitrosalicylic acid

The 1:1 proton‐transfer compound of the potent substituted amphetamine hallucinogen (R)‐2‐amino‐1‐(8‐bromobenzo[1,2‐b;5,4‐b′]difuran‐4‐yl)propane (common trivial name `bromodragonfly') with 3,5‐dinitrosalicylic acid, namely 1‐(8‐bromobenzo[1,2‐b;5,4‐b′]difuran‐4‐yl)propan‐2‐aminium 2‐carboxy‐4,6‐dinitrophenolate, C₁₃H₁₃BrNO₂⁺·C₇H₃N₂O₇⁻, forms hydrogen‐bonded cation–anion chain substructures comprising undulating head‐to‐tail anion chains formed through C(8) carboxyl–nitro O—H...O associations and incorporating the aminium groups of the cations. The intrachain cation–anion hydrogen‐bonding associations feature proximal cyclic R₃³(8) interactions involving both an N⁺—H...O_phenolate and the carboxyl–nitro O—H...O associations and aromatic π–π ring interactions [minimum ring centroid separation = 3.566 (2) Å]. A lateral hydrogen‐bonding interaction between the third aminium H atom and a carboxyl O‐atom acceptor links the chain substructures, giving a two‐dimensional sheet structure. This determination represents the first of any form of this compound and is in the (R) absolute configuration. The atypical crystal stability is attributed both to the hydrogen‐bonded chain substructures provided by the anions, which accommodate the aminium proton‐donor groups of the cations and give crosslinking, and to the presence of the cation–anion aromatic ring π–π interactions.     

Preparation and Stereochemistry of the Isopropylidene Derivatives of 1,2‐Dihydronaphtho[2,1‐b]Furan‐1,2‐Diol and 1,2,9,10‐Tetrahydronaphtho[2,1‐b:7,8‐b′] Difuran‐1,2,9,10‐Tetraol in Comparison with the Corresponding Acetyl Derivatives

Abstract

1,2‐Dihydronaphtho[2,1‐b]furan‐1,2‐diol and 1,2,9,10‐tetrahydronaphtho[2,1‐b:7,8‐b′]difuran‐1,2,9,10‐tetraol were transformed into the corresponding isopropylidene derivatives, which were studied mainly by ¹H NMR and chiral HPLC analyses in terms of a possible transformation mechanism and stereochemistry in comparison with their corresponding acetyl derivatives.     

Carbazolyl Benzo[1,2‐b:4,5‐b′]difuran: An Ambipolar Host Material for Full‐Color Organic Light‐Emitting Diodes

We have designed an ambipolar material, 3,7‐bis[4‐(N‐carbazolyl)‐phenyl]‐2,6‐diphenylbenzo[1,2‐b:4,5‐b′]difuran (CZBDF), and synthesized it by zinc‐mediated double cyclization. Its physical properties clarified that CZBDF possesses a wide‐gap character, well‐balanced and high hole and electron mobilities of larger than 10^?3 cm² V^?1 s^?1, and a high thermal stability. Using CZBDF as a host material for heterojunction OLED devices, a full range of visible emission was obtained. Notably, CZBDF also enabled us to fabricate RGB‐emitting homojunction OLEDs, with performances comparable or superior to the heterojunction devices composed of several materials.     

Medium band gap conjugated polymers from thienoacene derivatives and pentacyclic aromatic lactam as promising alternatives of poly(3‐hexylthiophene) in photovoltaic application

Two alternating medium band gap conjugated polymers (PBDT‐TPTI and PDTBDT‐TPTI) derived from 4,8‐bis(4,5‐dioctylthien‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene (BDT‐T) or 5,10‐bis(4,5‐didecylthien‐2‐yl)dithieno[2,3‐d:2′,3′‐d′]benzo[1,2‐b:4,5‐b′]dithiophene (DTBDT‐T) with pentacyclic aromatic lactam of N,N‐didodecylthieno[2′,3′:5,6]pyrido[3,4‐g]thieno[3,2‐c]‐iso‐quinoline‐5,11‐dione (TPTI), are synthesized and characterized. The comparative investigation of the photostabilities of the copolymers revealed that the PDTBDT‐TPTI film exhibited the comparable photostability in relative to P3HT. Meanwhile, the inverted photovoltaic cells (i‐PVCs) from the blend films of PBDT‐TPTI and/or PDTBDT‐TPTI with PC₇₁BM, in which poly[(9,9‐bis(3′‐(N,N‐dimethylamino)propyl)‐2,7‐fluorene)‐alt‐2,7‐(9,9‐dioctylfluorene)] were used as cathode modifying interlayer, presented higher power conversion efficiencies (PCEs) of 5.98% and 6.05% with photocurrent response ranging from 300 nm to 650 nm in contrast with the PCEs of 4.48% for the optimal inverted PVCs from P3HT/PC₇₁BM under AM 1.5 G 100 mW/cm². The PCEs of the i‐PVCs from PBDT‐TPTI and PDTBDT‐TPTI were improved to 7.58% and 6.91% in contrast to that of 0.02% for the P3HT‐based i‐PVCs, and the photocurrent responses of the devices were extended to 300–792 nm, when the ITIC was used as electron acceptor materials. The results indicate that the PBDT‐TPTI and PDTBDT‐TPTI can be used as the promising alternatives of notable P3HT in the photovoltaic application. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 85–95     

Development of New Two‐Dimensional Small Molecules Based on Benzodifuran for Efficient Organic Solar Cells

A new organic small molecule, DCA3TBDF, with a 2D benzo[1,2‐b:4,5‐b′]difuran (BDF) moiety as the central core and octyl cyanoacetate units as the end‐capped blocks, was designed and synthesized for solution‐processed bulk heterojunction solar cells. DCA3TBDF possesses good solubility in common organic solvents such as toluene, CH₂Cl₂, chlorobenzene, and CHCl₃ and good thermal stability with an onset decomposition temperature with 5 % weight‐loss occurring at 361 °C. The DCA3TBDF thin film showed a broad absorption at λ=320–700 nm and high crystallinity. Small‐molecule organic solar cells based on DCA3TBDF and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester demonstrated promising power conversion efficiency with a high fill factor under the illumination of AM 1.5G (100 mW cm^?2).     

Synthesis and Characterization of Planar Five‐Ring‐Fused Dithiophene‐dione

A series of new organic semiconductors based on s‐indaceno[1,2‐b:5,6‐b′]dithiophene‐4,9‐dione was successfully synthesized and characterized. The electron withdrawing carbonyl group lowers the LUMO energy levels, leading to increased electronegativities, which is beneficial for high photo‐stability in air. The n‐alkyl substituted compounds, 1c and 1d , crystallize with the rigid coplanar systems packed into slipped face‐to‐face π‐stacks. Interestingly, 1c and 1d also show liquid crystalline behaviors, which give highly ordered molecular packing over large area.     

Reactions of alkyl (z)‐2‐[(E)‐2‐ethoxycarbonyl‐2‐(2‐pyridinyl)‐ethenyl]amino‐3‐dimethylaminopropenoates with C‐ and N‐nucleophiles. the synthesis of fused pyranones,pyridinones and pyrimidinones

Alkyl 2‐[2‐ethoxycarbonyl‐2‐(2‐pyridinyl)ethenyl]amino‐3‐dimethylaminopropenoates 3 and 4 were transformed with C‐and N‐nucleophiles into β‐heteroaryl‐α,β‐didehydro‐α‐amino acid derivatives 13 ‐ 16 , substituted 3‐amino‐4H‐quinolizin‐4‐one 17, 2H,5H‐benzo[b]pyran‐2,5‐dione 18 and 19 , 2H,5H‐pyrano[4,3‐b]pyran‐2,5‐dione 20 , 2H,5H‐pyrano[3,2‐c]benzo[b]pyran‐2,5‐dione 21 , 2H‐1‐benzopyran‐2‐one 22 and 24 , pyrido[l,2‐a]pyrimidin‐4‐one 31–34 and 39 derivatives, and N‐heteroaryl‐1H‐imidazole‐4‐carboxylates 37 and 38 .     

Synthesis and photovoltaic performance of donor–acceptor polymers containing benzo[1,2‐b:4,5‐b′]dithiophene with thienyl substituents

Three alternating donor–acceptor copolymers have been synthesized by Stille coupling polymerization of 2,6‐(trimethyltin)?4,8‐bis(5‐dodecylthiophene‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene with 1,3‐dibromo‐5‐hexylthieno[3,4‐c]pyrrole‐4,6‐dione, 4,7‐dibromo‐1,3‐benzothiadiazole, and 5,7‐dibromo‐2,3‐didodecylthieno[3,4‐b]pyrazine, respectively. The synthesized polymers were tested in bulk heterojunction solar cells as blends with the acceptor [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM). The thienopyrroledione copolymer displayed a power conversion efficiency of 3.00% which was increased to 3.86% by application of the additive 1,8‐diiodooctane (DIO). Tapping mode atomic force microscopy analysis indicated that there was an increase in the phase separation between polymer and PCBM, leading to an improvement in the performance upon the addition of DIO. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2622–2630     

Angular polycyclic thiophenes containing two thiophene rings. Part II

The syntheses of naphtho[1,2–6:7,6-b′]bisbenzo[b]thiophene ( 4 ), naphtho[1,2–6:7,8-b′]bisbenzo[b]thiophene ( 5 ), naphtho[2,1-b:7,6-b′]bisbenzo[b]thiophene ( 8 ), naphtho[2,1-b:7,8-b′]bisbenzo[b]thiophene ( 9 ), naphtho-[1,2–6:5,6-b′]bisbenzo[b]thiophene ( 14 ), naphtho[1,2–6:6,5-b]bisbenzo[b]thiophene ( 17 ) and naphtho[2,1–6:-6,5-b′]bisbenzo[b]thiophene ( 23 ) are reported.     

Diels‐alder reactions of 2‐(2‐nitroethenyl)‐1H‐pyrroles and their oxygen and sulfur analogs with quinones

Diels‐Alder reaction of 2‐(E‐2‐nitroethenyl)‐1H‐pyrrole ( 2a ) with 1,4‐benzoquinone gave the desired benzo[e]indole‐6, 9(3H)‐dione ( 4a ) in 10% yield versus a 26% yield (lit. 86% [5]) of the known N‐methyl compound ( 4b ) from the N‐(or 1)‐methyl compound ( 2b ). Protection of the nitrogen of 2a with a phenylsul‐fonyl group ( 2c ) gave a 9% yield of the corresponding N‐(or 3)‐phenylsulfonyl compound ( 4c ). The reaction of 2b with 1,4‐naphthoquinone gave in 6% yield (lit. 64% [5]) the known 3‐methylnaphtho[2,3‐e]‐indole‐6, 9(3H)‐dione ( 6 ). The reaction of 2‐(E‐2‐nitroethenyl)furan ( 8a ) gave a small yield of the desired naphtho[2,1‐b]furan‐6, 9‐dione ( 9a ), recognized by comparing its NMR spectrum with that of 4b. The corresponding reaction of 2‐(E‐2‐nitroethenyl)thiophene ( 8b ) gave a 4% yield of naphtho[2,1‐ b ]thiophene‐6,9‐dione ( 9b ), previously prepared in 24% yield [12] in a three‐step procedure involving 2‐ethenylthiophene. Introducing an electron‐releasing 2‐methyl substituent into 8a and 8b gave 12a and 12b , which, upon reaction with 1,4‐benzoquinone, gave 2‐methylnaphtho[2,1‐b]furan‐6, 9‐dione ( 13a ) and its sulfur analog ( 13b ) in yields of 4 and 8%, respectively.     

Photophysics of a Coumarin in Different Solvents: Use of Different Solvatochromic Models

This study reported the photophysics of 7‐(diethylamino)coumarin‐3‐carboxylic acid N‐succinimidyl ester (7‐DCCAE) in different neat solvents of varying polarity using steady‐state absorption, fluorescence emission and picosecond time‐resolved spectroscopy. In nonpolar solvents, the dye molecule predominantly exists in nonpolar structure and exhibits very low value of nonradiative decay rate constant (k_nr), demonstrating the emission takes place from S₁‐LE to S₀ ground state. The fluorescence quantum yields, lifetime values of 7‐DCCAE in different solvents are rationalized on the basis of intramolecular charge transfer (ICT) followed by twisted intramolecular charge transfer state formation (TICT) as well as specific solute–solvent interactions. Several solvatochromic models (such as Lippert, Dimroth, Kamlet–Taft, Catalán 3P and Catalán 4P models) were used to analyze the solvatochromic shift of 7‐DCCAE in different solvents. The different empirical models show that the observed results are better correlate for nonchlorinated solvents and provide statistically significant best‐fit result. A comparison was done between comparatively new solvatochromic model (Catalán 3P and Catalán 4P model) with Kamlet–Taft model. The ground state structure of the said molecule was optimized by using Density Functional Theory (DFT).     

N,N‐dimethylamino‐functionalized basic ionic liquid catalyzed one‐pot multicomponent reaction for the synthesis of 4H‐benzo[b]pyran derivatives under solvent‐free condition

A simple, clean, and environmentally benign three‐component process for the synthesis of 4H‐benzo[b]pyran derivatives using basic ionic liquid N,N‐dimethylaminoethylbenzyldimethylammonium chloride ([PhCH₂Me₂N⁺CH₂CH₂NMe₂]Cl⁻) as an efficient catalyst under solvent‐free condition is described. A wide range of aromatic aldehydes easily undergoes condensation with malononitrile and 5,5‐dimethylcyclohexane‐1,3‐dione (dimedone) under solvent‐free condition to afford the desired products of good purity in excellent yields. Taking into account environmental and economical considerations, the protocol presented here has the merits of environmentally benign, simple operation, convenient workup, and good yields. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:91–94, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20516     

Synthesis of Some New Pyridine and Pyrimidine Derivatives Containing Benzothiazole Moiety

A variety of pyridine and pyrimidine rings incorporating benzothiazole moiety were synthesized by reaction of 1‐(2‐benzothiazolyl)‐1‐cyano‐3‐chloroacetone ( 1 ) with 2‐pyridone, 2‐thioxopyridine, thiouracil, and 2‐thioxopyrimidine derivatives to give compounds 7,9‐dimethylfuro[2,3‐b:4,5‐b′]dipyridin‐4‐ol 5 , 4, 6‐diphenylthieno[2,3‐b]pyridin‐2‐yl 9 , 2‐(benzo[d]thiazol‐2‐yl)‐2‐(7‐substituted‐5‐oxo‐5H‐thiazolo[3,2‐a]pyrimidin‐3‐yl)acetonitriles 12a and 12b , pyrimido[2,1‐b][1,3]thiazepine‐3‐carboxamide 15 , and benzo[4,5]thiazolo[3,2‐b]pyridazine‐3‐one 20 , respectively.     

Synthesis of spiro‐pyrazole‐3,3′‐thiopyrano[2,3‐b]pyridines and azolo[a]pyrido[2′,3′:5,6]thiopyrano[3,4‐d]pyrimidines as new ring systems with antifungal and antibacterial activities

Reactions of 2,3‐dihydro‐4‐oxo‐thiopyrano[2,3‐b]pyridine with aldehydes and with DMF‐DMA furnished the 3‐benzylidene and 3‐(N,N‐dimethylamino)‐methylene derivatives. The latter products afforded spiro‐pyrazolo‐3,3′‐thiopyrano[2,3‐b]pyridines and new tetra‐ and penta‐heterocyclic ring systems when treated with nitrilimines and aminoazoles, respectively. A number of the products showed high antifungal and antibacterial activities.     

Synthesis of novel 5H‐Pyrimido[5,4‐b]mdole‐(1H,3H)2,4‐diones as potential ligands for the cloned α1‐adrenoceptor subtypes

A new series of 3‐[ω‐[4‐(4‐substituted phenyl)piperazin‐1‐yl]alkyl]‐5H‐pyrimido[5,4‐b]indole‐(1H,3H)‐2,4‐diones ( 3–10 and 12–13 ) were synthesized from the N‐(2‐chloroethyl)‐N'‐[3‐(2‐ethoxycarbonyl)indolyl] urea ( 1 ) or the N‐(3‐chloropropyl)‐N'‐[3‐(2‐ethoxycarbonyl)indolyl] urea ( 2 ) and a number of 1‐(4‐substi‐tuted‐phenyl)piperazines. 3‐[2‐[4‐(4‐Aminophenyl)piperazin‐1‐yl]ethyl]‐5H‐pyrimido[5,4‐b]indole‐(1H,3H)2,4‐dione ( 14 ) was obtained by reduction of the parent nitro compound 8 . The obtained 5H‐pyrimido[5,4‐b]indole‐(1H,3H)2,4‐dione derivatives were tested towards cloned α_1A, α_1B and α_1D adrenergic receptors subtypes in binding assays. Some compounds showed good affinity and selectivity for the α_1D‐adrenoceptor subtype.     

Two similarly substituted benzo[h]pyrazolo[3,4‐b]quinoline‐5,6(10H)‐diones: supramolecular structures in two and three dimensions

The molecules of 8‐methyl‐7,10‐diphenyl‐5H‐benzo[h]pyrazolo[3,4‐b]quinoline‐5,6(10H)‐dione, C₂₇H₁₇N₃O₂, (I), are weakly linked into chains by a single C—H...O hydrogen bond, and these chains are linked into sheets by a π–π stacking interaction involving pyridyl and aryl rings. In 8‐methyl‐7‐(4‐methylphenyl)‐10‐phenyl‐5H‐benzo[h]pyrazolo[3,4‐b]quinoline‐5,6(10H)‐dione, C₂₈H₁₉N₃O₂, (II), the molecules are linked into a three‐dimensional framework structure by a combination of C—H...N, C—H...O and C—H...π(arene) hydrogen bonds, together with a π–π stacking interaction analogous to that in (I).     

Iminophosphine palladium(II) complexes: synthesis,characterization, and application in Heck cross‐coupling reaction of aryl bromides

Palladium(II) complexes containing phosphorus and nitrogen donor atoms (iminophosphine), dichlorido{N‐[2‐(diphenylphosphino)benzylidene]‐2‐trifluoromethylaniline}palladium(II) 1 , dichlorido{N‐[2‐(diphenylphosphino)benzylidene]‐3‐trifluoromethylaniline}palladium(II) 2 , dichlorido{N‐[2‐(diphenylphosphino)benzylidene]‐2‐methylaniline}palladium(II) 3 , dichlorido{N‐[2‐(diphenylphosphino)benzylidene]‐3‐methylaniline}palladium(II) 4 have been successfully synthesized and fully characterized by FT‐IR and NMR (¹H, ³¹P, ¹⁹F, and ¹³C) spectroscopy techniques. These complexes were first step tested in the reaction of bromobenzene and styrene to determine the optimal coupling reaction conditions and then successfully applied as catalysts for Heck cross‐coupling reactions of activated and deactivated aryl bromides with styrene derivatives and several acrylates. Copyright © 2014 John Wiley & Sons, Ltd.     

Recent Progress in All‐Polymer Solar Cells Based on Wide‐Bandgap p‐Type Polymers

All‐polymer solar cells (all‐PSCs), with the photoactive layer exclusively composed of polymers as both donor and acceptor, have attracted growing attention due to their unique merits in optical, thermal and mechanical durability. Through the combined strategies in materials design and device engineering, recently the power conversion efficiencies of single‐junction all‐PSCs have been boosted up to 11 %. This review focuses on the recent progress of all‐PSCs comprising of wide band‐gap p‐type polymers, especially those based on the units of thieno[3,4‐c]pyrrole‐4,6(5H)‐dione], fluorinated benzotriazole, benzo[1,2‐c:4,5‐c′]dithiophene‐4,8‐dione, and pyrrolo[3,4‐f]benzotriazole‐5,7(6H)‐dione. Meantime, several categories of n‐type polymers used to match with these polymer donors are also reviewed. Finally, a brief summary of the strategies of molecular design and morphology optimization is given, and strategies toward further improving performance of all‐PSCs are outlined.     

A New Four‐Component Reaction for the Synthesis of Spiro[4H‐indeno[1,2‐b]pyridine‐4,3′‐[3H]indoles]

A new four‐component synthesis of spiro[4H‐indeno[1,2‐b]pyridine‐4,3′‐[3H]indoles] and spiro[acenaphthylene‐1(2H),4′‐[4H‐indeno[1,2‐b]pyridines] by the reaction of indane‐1,3‐dione, 1,3‐dicarbonyl compounds, isatins (=1H‐indole‐2,3‐diones) or acenaphthylene‐1,2‐dione, and AcONH₄ in refluxing toluene in the presence of a catalytic amount of pyridine is reported.