Synthesis and spectroelectrochemistry of dithieno(3,2‐b:2′,3′‐d)pyrrole derivatives

New π‐conjugated polymers containing dithieno(3,2‐b:2′,3′‐d)pyrrole (DTP) were successfully synthesized via electropolymerization. The effect of structural differences on the electrochemical and optoelectronic properties of the 4‐[4H‐dithieno(3,2‐b:2′,3′‐d)pyrrol‐4‐yl]aniline (DTP–aryl–NH₂), 10‐[4H‐dithiyeno(3,2‐b:2′,3′‐d)pirol‐4‐il]dekan‐1‐amine (DTP–alkyl–NH₂), and 1,10‐bis[4H‐dithieno(3,2‐b:2′,3′‐d)pyrrol‐4‐yl] decane (DTP–alkyl–DTP) were investigated. The corresponding polymers were characterized by cyclic voltammetry, NMR (¹H‐NMR and ¹³C‐NMR), and ultraviolet–visible spectroscopy. Changes in the electronic nature of the functional groups led to variations in the electrochemical properties of the π‐conjugated systems. The electroactive polymer films revealed redox couples and exhibited electrochromic behavior. The replacement of the DTP–alkyl–DTP unit with DTP–aryl–NH₂ and DTP–alkyl–NH₂ resulted in a lower oxidation potential. Both the poly(10‐(4H‐Dithiyeno[3,2‐b:2′,3′‐d]pirol‐4‐il)dekan‐1‐amin) (poly(DTP–alkyl–NH₂)) and poly(1,10‐bis(4H‐dithieno[3,2‐b:2′,3′‐d]pyrrol‐4‐yl) decane) (poly(DTP–alkyl–DTP)) films showed multicolor electrochromism and also fast switching times (<1 s) in the visible and near infrared regions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40701.     

Crystallography and Structure–Property Relationships in 2,2′,2″,2′′′,4,4′,4″,4′′′,6,6′,6″,6′′′‐Dodecanitro‐1,1′ : 3′1″ : 3″,1′′′‐ Quaterphenyl (DODECA)

X‐ray crystallographic study of 2,2′,2″,2′′′,4,4′,4″,4′′′,6,6′,6″,6′′′‐dodecanitro‐1,1′ : 3′1″ : 3″,1′′′‐quaterphenyl (DODECA) has been carried out. Nonbonding interatomic distances of oxygen atoms inside of all the nitro groups are shorter than those corresponding to the intermolecular contact radii for oxygen. By means of the DFT B3LYP/6‐31(d, p) method a difference of 136 kJ mol⁻¹ between the X‐ray and DFT structures of DODECA was found. The bearer of the highest initiation reactivity in its molecule in solid phase should be the nitro group at 4′′′‐position, in contrast to those at 2′‐ or 2″‐positions in its isolated molecule. The most reactive nitro group in the DODECA molecule can be well specified by the relationship between net charges on nitro groups and charges on their nitrogen atoms, both of them for the X‐ray structure. The ¹⁵N chemical shift, corresponding to this nitro group for the initiation by impact and shock, correlates very well with these shifts of the reaction centers of the other six “genuine” polynitro arenes.     

Effect of monomer composition on properties of copolyimides derived from 3,3′,4,4′‐biphenyltetracarboxylic dianhydride/4,4′‐oxydianiline/1,3‐bis (4‐aminophenoxy)benzene

A series of uncontrolled molecular weight homopolyimides and copolyimides based on 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (s‐BPDA)/4,4′‐oxydianiline (4,4′‐ODA)/1,3‐bis(4‐aminophenoxy)benzene (TPER) were synthesized. All the polyimides displayed excellent thermal stability and mechanical properties, as evidenced by dynamic thermogravimetric analysis and tensile properties testing. A singular glass transition temperature (T_g) was found for each composite from either differential scanning calorimetry (DSC) or dynamic mechanical analysis (DMA), but the values determined from tan δ of DMA were much different from those determined from DSC and storage modulus (E′) of DMA. The Fox equation was used to estimate the random T_g values. Some composites exhibited re‐crystallization after quenching from the melt; upon heating, multi‐melting behavior was observed after isothermal crystallization at different temperatures. The equilibrium melting temperature was estimated using the Hoffman‐Weeks method. Additionally, DMA was conducted to obtain E′ and tan δ. Optical properties were strongly dependent on the monomer composition as evidenced by UV‐visible spectra. X‐ray diffraction was used to interpret the crystal structure. All the results indicated that composites with TPER composition ≥ 70% were dominated by the TPER/s‐BPDA polyimide phase, and ≤40% by the 4,4′‐ODA/s‐BPDA polyimide phase. When the ratio between the two diamines was close to 1:1, the properties of the copolyimides were very irregular, which means a complicated internal structure. Copyright © 2011 Society of Chemical Industry     

Synthesis of 3′,4′‐disubstituted terthiophenes. Characterization and electropolymerization. I. 3′,4′‐dibromo‐2,2′:5′,2″‐terthiophene in photovoltaic display

Recent studies on conducting polymers have demonstrated that polymers of 3‐substituted thiophene produce very stable compounds. Although this kind of substitution improves the regularity, structural defects still exist. To overcome this drawback, the polymerization of 3,4‐disubstituted thiophene is proposed as a convenient way of synthesizing regular, highly conjugated conductive polymers. Our interest is thus focused on the synthesis of tetra‐substituted thiophene derivatives, their polymerization, electrochemical properties, spectral characteristics, oxidizing potential, and the feasibility of photocells development. In this article, we report the synthesis and characterization of 3′,4′‐dibromo‐2,2′:5′,2″‐terthiophene which, as such or modified, may be a good starting product for obtaining new monomers of 3′,4′‐disubstituted terthiophenes, that would allow the effect of the substituents on the properties of the respective polymers to be studied. In addition, the monomer was electropolymerized and the resulting deposit was electrochemically and morphologically characterized. Two conclusions were drawn: first, more uniform and homogeneous layers than those of polythiophene are obtained; second, the thin layers of the polymer, electron acceptors, absorb in the visible. Finally, photocells were assembled to investigate their photovoltaic effect. Although the so prepared solar cells showed some photovoltaic effect, the yield was low.© 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5314–5321, 2006     

Soluble and light‐colored polyimides from 2,3,2′,3′‐oxydiphthalic anhydride and aromatic diamines

A series of polyimides were prepared from 2,3,2′,3′‐oxydiphthalic anhydride (3,3′‐ODPA) with various aromatic diamines via three different synthetic procedures. The one‐step and two‐step methods with the thermal imidization of poly(amic acids) (PAAs) yielded polyimides with a relatively low inherent viscosity; these produced brittle films. The polyimides prepared by the two‐step method via the chemical imidization of PAA precursors exhibited a higher inherent viscosity and afforded tough and creaseable films. All the 3,3′‐ODPA based polyimides had a significantly higher solubility than the corresponding polyimides from 3,4,3′,4′‐oxydiphthalic anhydride. The films cast from 3,3′‐ODPA polyimides also showed high optical transparencies and less color, with an ultraviolet–visible absorption edge of 370–397 nm and low yellowness index values of 11.3–29.8. These polyimides exhibited glass‐transition temperatures in the range 211–289°C and showed no significant decomposition below 500°C under nitrogen or air atmospheres. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1352–1360, 2005     

Crystallography and Structure–Property Relationships of 2,2″,4,4′,4″,6,6′,6″‐Octanitro‐1,1′ : 3′,1″‐Terphenyl (ONT)

An X‐ray crystallographic study of 2,2″,4,4′,4″,6,6′,6″‐octanitro‐1,1′ : 3′,1″‐terphenyl (ONT) has been carried out. The dihedral angles between benzene rings vary from 84.9° to 89.4°. Nonbinding interatomic distances of oxygen atoms inside all the nitro groups are shorter than the intermolecular contact radii for oxygen. On the basis of the DFT B3LYP/6‐31(d, p) method it was found that the difference between the X‐ray structure in the solid phase and DFT result for the gas phase is 98 kJ mol⁻¹, and the bearer of the highest initiation reactivity of the ONT molecule in the solid phase should be the nitro group at 4″‐position, in contrast to those at 4′‐ or 6′‐position that play this role in the isolated molecule. It has been stated that the nitro groups at the reaction centers of the ONT molecule are relatively well specified by their ¹⁵N NMR chemical shifts.     

Morphology,mechanical property,and modeling evaluation of P(3HB‐co‐4HB)/nano‐ZnO composites

Poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) (P(3HB‐co‐4HB)) and nanometer zinc oxide (nano‐ZnO) modified by solid titanate coupling agent (TMC980) were selected to prepare P(3HB‐co‐4HB)/nano‐ZnO composites via melt blending. Scanning electron microscope (SEM), capillary rheometer, polarized optical microscopy (POM), and universal testing machine were used to characterize the fracture morphology, rheological property, spherulitic morphology, and mechanical properties of P(3HB‐co‐4HB)/nano‐ZnO composites. Halpin‐Tsai equation was used to quantitatively evaluate the dispersion and enhancement effects of modified nano‐ZnO on P(3HB‐co‐4HB). The results demonstrated that modified nano‐ZnO at 0.2%∼0.3% of volume fraction could significantly improve the tensile strength, elastic modulus and toughness, increase the melt viscosity, refine the spherulitic size, and rough the fracture morphology of P(3HB‐co‐4HB)/nano‐ZnO composites. Based on the effective aspect ratio (ξ) from Halpin‐Tsai model evaluation, the optimal dosage of nano‐ZnO for P(3HB‐co‐4HB)/nano‐ZnO composites was also at 0.2%∼0.3% of volume fraction. The Halpin‐Tsai equation was found to predict the experimental data most accurately for the P(3HB‐co‐4HB)/nano‐ZnO composites. POLYM. COMPOS., 37:3113–3121, 2016. © 2015 Society of Plastics Engineers     

Synthesis of Substituted 2,2′‐Bipyridines and 2,2′:6′,2′′‐Terpyridines by Cobalt‐Catalyzed Cycloaddition Reactions of Nitriles and α,ω‐Diynes with Exclusive Regioselectivity

A variety of substituted 2,2′‐bipyridines were synthesized by a 1,2‐bis(diphenylphosphino)ethane (dppe)/cobalt chloride hexahydrate (CoCl₂⋅6 H₂O)/zinc‐catalyzed [2+2+2] cycloaddition reaction of diynes and nitriles, with all reactions exhibiting exclusive regioselectivity. Thus, symmetrical and unsymmetrical 1,6‐diynes and 2‐cyanopyridine reacted in the presence of 5 mol % of dppe, 5 mol % of CoCl₂⋅6 H₂O and 10 mol % of zinc powder to provide the corresponding 2,2′‐bipyridines. Under identical reaction conditions, 1‐(2‐pyridyl)‐1,6‐diynes and nitriles reacted smoothly with exclusive regioselectivity to produce 2,2′‐bipyridines in good yield. 2,2′‐Bipyridines were also obtained by the double [2+2+2] cycloaddition reaction of 1,6,8,13‐tetraynes with nitriles. Similarly, 2,2′:6′,2′′‐terpyridines were synthesized from 1‐(2‐pyridyl)‐1,6‐diyne and 2‐cyanopyridine. The regiochemistry observed can be explained by considering the electronic nature of cobaltacyclopentadiene intermediates and nitriles. A survey of the exclusive regiochemical trend gives reasonable credence to the synthetic potential of the present method.     

Synthesis and hydrolysis study of polyacrylates containing 2′,5-dichloro-4′-nitrosalicylanilide

Monomers (meth)acryloyloxy-2′,5-dichloro-4′-nitrosalicylanilide have been synthesized by treating 2′,5-dichloro-4′-nitrosalicylanilide (niclosamide) with acryloyl or methacryloyl chloride, and polymerized by free radical polymerization to give a polymer containing chemically bonded niclosamide. The structure of monomer and polymer were confirmed by IR, UV, and elemental analysis. Hydrolysis data of polymer in different media indicated that the hydrolysis rates of polymer were strongly dependent on the nature of the polymer structure and the hydrolyzing medium. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 29–33, 1997     

Direct (hetero)arylation polymerization for the synthesis of donor–acceptor conjugated polymers based on N‐benzoyldithieno [3,2‐b:2′,3′‐d]pyrrole and diketopyrrolopyrrole toward organic photovoltaic cell application

In this research, new donor–acceptor (D‐A) photovoltaic polymers were synthesized from dithieno[3,2‐b:2′,3′‐d]pyrrole electron donor derivatives, including N‐benzoyldithieno[3,2‐b:2′,3′‐d]pyrrole and N‐(4‐hexylbenzoyl)dithieno[3,2‐b:2′,3′‐d]pyrrole, in combination with the electron deficient unit 2,5‐bis(2‐ethylhexyl)‐3,6‐di(thiophen‐2‐yl)‐2,5‐dihydropyrrolo[3,4‐c]pyrrole‐1,4‐dione via direct (hetero)arylation polymerization. The D‐A conjugated polymers obtained were characterized via ¹H NMR, gel permeation chromatography, Fourier transform infrared spectroscopy, DSC, XRD, photoluminescence and UV–visible methods. In addition, these D‐A polymers were used as activated layers in bilayer and bulk heterojunction structures for the fabrication of organic photovoltaic cells. © 2019 Society of Chemical Industry     

Nonenzymatic Oligomerization of 3′,5′‐Cyclic CMP Induced by Proton and UV Irradiation Hints at a Nonfastidious Origin of RNA

We report that 3′,5′‐cyclic CMP undergoes nonenzymatic di‐ and trimerization at 20 °C under dry conditions upon proton or UV irradiation. The reaction involves stacking of the cyclic monomers and subsequent polymerization through serial transphosphorylations between the stacked monomers. Proton‐ and UV‐induced oligomerization of 3′,5′‐cyclic CMP demonstrates that pyrimidines—similar to purines—might also have taken part in the spontaneous generation of RNA under plausible prebiotic conditions as well as in an extraterrestrial context. The observed polymerization of naturally occurring 3′,5′‐cyclic nucleotides supports the possibility that the extant genetic nucleic acids might have originated by way of a straight Occamian path, starting from simple reactions between plausibly preactivated monomers.     

Photoconductivity of 1,2‐(1′,1′,2′,2′‐tetracyanomethanoxymethano)[60]fullerene‐doped PVK

1,2‐(1′,1′,2′,2′‐Tetracyanomethanoxymethano)[60]fullerene, a derivative of C₆₀, is a better electron acceptor than the parent C₆₀. The film of PVK doped with 1.6 wt % of this derivative was prepared and characterized. The micromorphology of the film was studied by transmission electron microscopy (TEM) and high‐resolution transmission electron microscopy (HRTEM). The photoinduced discharge curves and photoconduction spectra of the films were measured. The results showed that PVK doped with the C₆₀ derivative displayed more photoconductivity than that of PVK doped with pure C₆₀ or a mixture of C₆₀ and C₇₀. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 209–213, 1999     

Enantioenriched Calcium‐(R)‐5,5′,6,6′,7,7′,8,8′‐Octahydro‐BINOL (H8‐BINOL): An Efficient Catalyst for the Creation of a Quaternary Stereocenter#

An efficient catalyst for the creation of a quaternary stereocenter has been developed utilizing easily available, eco‐friendly CaCl₂ and applied for enantioselective carbon‐carbon bond forming reactions. Among the surveyed ligands, it was found that (R)‐5,5′,6,6′,7,7′,8,8′‐octahydro‐BINOL‐Ca ( 2f ) gave maximum ee (72%) with excellent yields.     

Preparation and properties of transparent zinc oxide/silicone nanocomposites for the packaging of high‐power light‐emitting diodes

New transparent zinc oxide (ZnO)/silicone nanocomposites with outstanding integrated properties, including a high UV‐shielding efficiency and transparency, bigger thermal conductivity, and lower dielectric constant, were successfully developed; they were prepared by the uniform dispersion of organic modified nano‐ZnO in a silicone matrix through in situ polymerization. The ZnO precursor was prepared by a direct precipitation method, which was then calcinated at different temperatures to produce nano‐ZnO with various morphologies and sizes. The effects of the size, surface nature, and content of nano‐ZnO on the key properties (e.g., optical and dielectric properties, thermal conductivities) of the composites were systematically investigated. The results show that the organic nano‐ZnO prepared by 3‐methacryloxypropyltrimethoxysilane can increase the dispersion of nano‐ZnO in silicone resin, and the interfacial adhesion between inorganic and organic phases, and consequently improve the integrated properties of nanocomposites. The increase of the particle content and size of ZnO in composites can lead to high thermal conductivity and UV‐shielding efficiency but lower visible‐light transparency, so there is an optimum content and size of ZnO in composites to obtain the best integrated properties of the composites. Specifically, the nanocomposite containing 0.03 wt % organic nano‐ZnO with an average size of 46 ± 0.4 nm not only had a high visible‐light transparency, UV‐shielding efficiency, and thermal conductivity but also possessed a low dielectric constant and loss and met the requirements of high‐performance electronic packaging for high‐power light‐emitting diodes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Proton Conducting Membranes Based on Poly(2,2′‐imidazole‐5,5′‐bibenzimidazole)

Poly(2,2′‐imidazole‐5,5′‐bibenzimidazole) (PBI‐imi) was synthesized via the polycondensation between 3,3′,4,4′‐tetraaminobiphenyl and 4,5‐imidazole‐dicarboxylic acid. Effects of the reaction conditions on the intrinsic viscosity of the synthesized polymers were studied. The results show that the molecular weight of the polymers increases with increasing monomer concentration and reaction time, and then levels off. With higher reaction temperature, the molecular weight of the polymer is higher. With the additional imidazole group in the backbone, PBI‐imi shows improved phosphoric acid doping ability, as well as a little higher proton conductivity when compared with widely used poly[2,2′‐(m‐phenylene)‐5,5′‐bibenzimidazole] (PBI‐ph).Whereas, PBI‐imi and PBI‐ph have the similar chemical oxidation stability. PBI‐imi/3.0 H₃PO₄ composite membranes exhibit a proton conductivity as high as 10^–4 S cm^–1 at 150 °C under anhydrous condition. The temperature dependence of proton conductivity of acid doped PBI‐imi can be modeled by an Arrhenius equation.     

Synthesis of 3,3′-Bis(2,2′,4,4′,6,6′-Hexanitortilbene)

This paper describes the synthesis of 3,3′bis(2,2′,4,4′,6,6′-hexanitrostilbene) (5). Based on the Ullmann reaction we prepared the title compound in nitrobenzene by using 3-chloro 2,2′,4,4′,6,6′-hexanitroztilbene (4) as the starting material and copper powder as the catalyst. (4) was reacted with hydrazine, not to yield a desired product, azo-3,3′bist(2,2′,4,4′,6,6′-hexanitrostilbene.) but to form a well-known explosive, 2,2′,4,4′,6,6′-hexanitrostibene (6). Differential scanning calorimetrical analysis has shown that (5) begins to decompose at the temperature of 298°C.     

Effects of ball milling dispersion of nano‐SiOx particles on impact strength and crystallization behavior of nano‐SiOx–poly(phenylene sulfide) nanocomposites

Ball milling and mixing with strong shear force and strike force were applied to get fine dispersion of nano‐SiO_x particles in poly(phenylene sulfide) (PPS) powder. Nano‐SiO_x/PPS composites were manufactured by intensive compounding with 3 wt% nano‐SiO_x particles. Effects of the ball milling dispersion on crystal behavior and impact strength of nano‐SiO_x/PPS nanocomposites were studied. Physical mechanisms of ball milling dispersion were investigated. Evaluations based on both WAXD and DSC indicates that crystallization behavior of nano‐SiO_x/heat‐treated PPS (HT‐PPS) nanocomposites was influenced by the ball milling process. Their crystallinity was 25% less while Izod impact strength was 89% better than those of as‐received neat PPS. Increased kinetic energy via ball milling by external work makes nano‐SiO_x able to overcome the attraction from itself to prevent agglomeration. Interfacial bonding of two phases between nano‐SiO_x and PPS was enhanced by crosslinking in HT‐PPS and reduction in surface tension of interface during ball milling. The bonds allow SiO_x to dissipate energy and thus improve PPS impact strength from the addition of nano‐SiO_x. POLYM. ENG. SCI., 46:820–825, 2006. © 2006 Society of Plastics Engineers     

Organosoluble polyimides derived from asymmetric 2‐substituted‐and 2,2′,6‐trisubstituted‐4,4′‐oxydianilines

We report a new method for the preparation of asymmetric diamines using 4,4′‐oxydianiline (4,4′‐ODA) as the starting material. By controlling the equivalents of bromination agent, N‐bromosuccinimide, we were able to attach bromide and phenyl substituents at the 2‐ or 2,2′,6‐positions of 4,4′‐ODA. Thus, four new asymmetric aromatic diamines, 2‐bromo‐4,4′‐oxydianiline (6), 2,2′,6‐tribromo‐4,4′‐oxydianiline (7), 2‐phenyl‐4,4′‐oxydianiline (8) and 2,2′,6‐triphenyl‐4,4′‐oxydianiline (9), were synthesized by this method. Their structural asymmetry was confirmed using ¹H NMR spectroscopy. Asymmetric polyimides (PI10–PI13) were prepared from these diamines and three different dianhydrides (pyromellitic dianhydride (PMDA), 3,3′,4,4′‐biphenyltetracarboxylic dianhydride and 2,2‐bis(3,4‐dicarboxyphenyl)hexafluoropropane dianhydride) in refluxing m‐cresol. The formed polyimides, except PI10a derived from 6 and PMDA, were all soluble in m‐cresol without premature precipitation during polymerization. These polyimides with inherent viscosity of 0.41–0.96 dL g^?1, measured at a concentration of 0.5 g dL^?1 in N‐methyl‐2‐pyrrolidone at 30 °C, can form tough and flexible films. Because of the structural asymmetry, they also exhibited enhanced solubility in organic solvents. Especially, polyimides PI11a and PI13a derived from 7 and 9 with rigid PMDA were soluble in various organic solvents at room temperature. The structural asymmetry of the prepared polyimides was also evidenced from ¹H NMR spectroscopy. In the ¹H NMR spectrum of PI11a, the protons of pyromellitic moiety appeared in an area ratio of 1:2:1 at three different chemical shifts, which were assigned to head‐to‐head, head‐to‐tail and tail‐to‐tail configurations, respectively. These polyimides also exhibited good thermal stability. Their glass transition temperatures ranged from 297 to 344 °C measured using thermal mechanical analysis. © 2013 Society of Chemical Industry     

Synthesis and Cytostatic and Antiviral Activities of 2′‐Deoxy‐2′,2′‐difluororibo‐ and 2′‐Deoxy‐2′‐fluororibonucleosides Derived from 7‐(Het)aryl‐7‐deazaadenines

A series of sugar‐modified derivatives of cytostatic 7‐heteroaryl‐7‐deazaadenosines (2′‐deoxy‐2′‐fluororibo‐ and 2′‐deoxy‐2′,2′‐difluororibonucleosides) bearing an aryl or heteroaryl group at position 7 was prepared and screened for biological activity. The difluororibonucleosides were prepared by non‐ stereoselective glycosidation of 6‐chloro‐7‐deazapurine with benzoyl‐protected 2‐deoxy‐2,2‐difluoro‐D ‐erythro‐pentofuranosyl‐1‐mesylate, followed by amination and aqueous Suzuki cross‐couplings with (het)arylboronic acids. The fluororibo derivatives were prepared by aqueous palladium‐catalyzed cross‐coupling reactions of the corresponding 7‐iodo‐7‐deazaadenine 2′‐deoxy‐2′‐fluororibonucleoside 20 with (het)arylboronic acids. The key intermediate 20 was prepared by a six‐step sequence from the corresponding arabinonucleoside by selective protection of 3′‐ and 5′‐hydroxy groups with acid‐labile groups, followed by stereoselective S_N2 fluorination and deprotection. Some of the title nucleosides and 7‐iodo‐7‐deazaadenine intermediates showed micromolar cytostatic or anti‐HCV activity. The most active were 7‐iodo and 7‐ethynyl derivatives. The corresponding 2′‐deoxy‐2′,2′‐difluororibonucleoside 5′‐O‐triphosphates were found to be good substrates for bacterial DNA polymerases, but are inhibitors of human polymerase α.