Controlling the electrical characteristics of Au/n‐Si structure with and without (biphenyl‐CoPc) and (OHSubs‐ZnPc) interfacial layers at room temperature

In order to interpret well whether or not the organic or polymer interfacial layer is effective on performance of the conventional Au/n‐Si (metal semiconductor [MS]) type Schottky barrier diodes (SBDs), in respect to ideality factor (n ), leakage current, rectifying rate (RR ), series and shunt resistances (R_s , R_sh ) and surface states (N_ss ) at room temperature, both Au/biphenyl‐CoPc/n‐Si (MPS₁) and Au/OHSubs‐ZnPc/n‐Si (MPS₂) type SBDs were fabricated. The electrical characteristics of these devices have been investigated and compared by using forward and reverse bias current–voltage (I–V ) characteristics in the voltage range of (?4 V)–(4 V) for with and without (biphenyl‐CoPc) and (OHSubs‐ZnPc) interfacial layers at room temperature. The main electrical parameters of these diodes such as reverse saturation current (I₀ ), ideality factor (n ), zero‐bias barrier height (Φ_B0 ), RR , R_s and R_sh were found as 1.14 × 10^?5 A, 5.8, 0.6 eV, 362, 44 Ω and 15.9 kΩ for reference sample (MS), 7.05 × 10^?10 A, 3.8, 0.84 eV, 2360, 115 Ω and 270 kΩ for MPS1 and 2.16 × 10^?7 A, 4.8, 0.7 eV, 3903, 62 Ω and 242 kΩ for MPS₂, respectively. It is clear that all of these parameters considerably change by using an organic interfacial layer. The energy density distribution profile of N_ss was found for each sample by taking into account the voltage dependence of effective barrier height (Φ_e ) and ideality factor, and they were compared. Experimental results confirmed that the use of biphenyl‐CoPc and OHSubs‐ZnPc interfacial layer has led to an important increase in the performance of the conventional of MS type SBD. Copyright © 2015 John Wiley & Sons, Ltd.     

Enhanced Electrocatalytic Performance of a Porous g‐C3N4/Graphene Composite as a Counter Electrode for Dye‐Sensitized Solar Cells

A porous graphitic carbon nitride (g‐C₃N₄)/graphene composite was prepared by a simple hydrothermal method and explored as the counter electrode of dye‐sensitized solar cells (DSCs). The obtained g‐C₃N₄/graphene composite was characterized by XRD, SEM, TEM, FTIR spectroscopy, and X‐ray photoelectron spectroscopy. The results show that incorporating graphene nanosheets into g‐C₃N₄ forms a three‐dimensional architecture with a high surface area, porous structure, efficient electron‐transport network, and fast charge‐transfer kinetics at the g‐C₃N₄/graphene interfaces. These properties result in more electrocatalytic active sites and facilitate electrolyte diffusion and electron transport in the porous framework. As a result, the as‐prepared porous g‐C₃N₄/graphene composite exhibits an excellent electrocatalytic activity. In I^?/I₃^? redox electrolyte, the charge‐transfer resistance of the porous g‐C₃N₄/graphene composite electrode is 1.8 Ω cm², which is much lower than those of individual g‐C₃N₄ (70.1 Ω cm²) and graphene (32.4 Ω cm²) electrodes. This enhanced electrocatalytic performance is beneficial for improving the photovoltaic performance of DSCs. By employing the porous g‐C₃N₄/graphene composite as the counter electrode, the DSC achieves a conversion efficiency of 7.13 %. This efficiency is comparable to 7.37 % for a cell with a platinum counter electrode.     

High‐Efficiency Oxygen Reduction to Hydrogen Peroxide Catalyzed by Nickel Single‐Atom Catalysts with Tetradentate N2O2 Coordination in a Three‐Phase Flow Cell

Carbon‐supported Ni^II single‐atom catalysts with a tetradentate Ni‐N₂O₂ coordination formed by a Schiff base ligand‐mediated pyrolysis strategy are presented. A Ni^II complex of the Schiff base ligand (R,R)‐(?)‐N,N′‐bis(3,5‐di‐tert‐butylsalicylidene)‐1,2‐cyclohexanediamine was adsorbed onto a carbon black support, followed by pyrolysis of the modified carbon material at 300 °C in Ar. The Ni‐N₂O₂/C catalyst showed excellent performance for the electrocatalytic reduction of O₂ to H₂O₂ through a two‐electron transfer process in alkaline conditions, with a H₂O₂ selectivity of 96 %. At a current density of 70 mA cm^?2, a H₂O₂ production rate of 5.9 mol g_cat.^?1 h^?1 was achieved using a three‐phase flow cell, with good catalyst stability maintained over 8 h of testing. The Ni‐N₂O₂/C catalyst could electrocatalytically reduce O₂ in air to H₂O₂ at a high current density, still affording a high H₂O₂ selectivity (>90 %). A precise Ni‐N₂O₂ coordination was key to the performance.     

Growth of poly(3,4‐ethylenedioxythiophene) films prepared by base‐inhibited vapor phase polymerization

Transparent [90% transmittance at 550 nm at a sheet resistance (R_s) of 279 Ω sq^?1] poly(3,4‐ethylenedioxythiophene) (PEDOT) films with electrical conductivities up to 1354 S cm^?1 are prepared using base‐inhibited vapor phase polymerization at atmospheric pressure. The influence of reaction conditions, such as temperature and growth time, on the film formation is investigated. A simple and convenient two‐electrode method is used for the in situ measurement of resistance, enabling to investigate the growth mechanism of polymer films and the influence of different parameters (relative humidity and the amount of oxidant) on the film growth. Low humidity exerts a detrimental effect on film growth and conductivity. In situ R_s measurements suggest that a large structural change occurs upon washing the PEDOT‐oxidant film. © 2014 Wiley Periodicals, Inc. J Polym Sci Part B: Polym. Phys. 2014 , 52, 561–571     

Development and Investigation of a NASICON‐Type High‐Voltage Cathode Material for High‐Power Sodium‐Ion Batteries

Herein, we introduce a 4.0 V class high‐voltage cathode material with a newly recognized sodium superionic conductor (NASICON)‐type structure with cubic symmetry (space group P2₁3), Na₃V(PO₃)₃N. We synthesize an N‐doped graphene oxide‐wrapped Na₃V(PO₃)₃N composite with a uniform carbon coating layer, which shows excellent rate performance and outstanding cycling stability. Its air/water stability and all‐climate performance were carefully investigated. A near‐zero volume change (ca. 0.40 %) was observed for the first time based on in situ synchrotron X‐ray diffraction, and the in situ X‐ray absorption spectra revealed the V^3.2+/V^4.2+ redox reaction with high reversibility. Its 3D sodium diffusion pathways were demonstrated with distinctive low energy barriers. Our results indicate that this high‐voltage NASICON‐type Na₃V(PO₃)₃N composite is a competitive cathode material for sodium‐ion batteries and will receive more attention and studies in the future.     

Versatile p‐Type Chemical Doping to Achieve Ideal Flexible Graphene Electrodes

We report effective solution‐processed chemical p‐type doping of graphene using trifluoromethanesulfonic acid (CF₃SO₃H, TFMS), that can provide essential requirements to approach an ideal flexible graphene anode for practical applications: i) high optical transmittance, ii) low sheet resistance (70 % decrease), iii) high work function (0.83 eV increase), iv) smooth surface, and iv) air‐stability at the same time. The TFMS‐doped graphene formed nearly ohmic contact with a conventional organic hole transporting layer, and a green phosphorescent organic light‐emitting diode with the TFMS‐doped graphene anode showed lower operating voltage, and higher device efficiencies (104.1 cd A^?1, 80.7 lm W^?1) than those with conventional ITO (84.8 cd A^?1, 73.8 lm W^?1).     

Layer‐by‐layer Assembled Multilayers of Graphene/Mono‐(6‐amino‐6‐deoxy)‐β‐cyclodextrin for Detection of Dopamine

Graphene/mono‐(6‐amino‐6‐deoxy)‐β‐cyclodextrin multilayer films composed of graphene sheet (GS) and mono‐(6‐amino‐6‐deoxy)‐β‐cyclodextrin (NH₂‐β‐CD) were fabricated easily by two steps. First, negatively charged graphene oxide (GO) and positively charged mono‐(6‐amino‐6‐deoxy)‐β‐cyclodextrin (NH₂‐β‐CD) were layer‐by‐layer (LBL) self‐assembled on glassy carbon electrode (GCE) modified with a layer of poly(diallyldimethylammonium chloride) (PDDA). Then graphene/mono‐(6‐amino‐6‐deoxy)‐β‐cyclodextrin (GS/NH₂‐β‐CD) multilayer films were built up by electrochemical reduction of graphene oxide/mono‐(6‐amino‐6‐deoxy)‐β‐cyclodextrin (GO/NH₂‐β‐CD). Combining the high surface area of GS and the active recognition sites on β‐cyclodextrin (β‐CD), the GS/NH₂‐β‐CD multilayer films show excellent electrochemical sensing performance for the detection of DA with an extraordinary broad linear range from 2.53 to 980.05 µmol·L^?1. This study offers a simple route to the controllable formation of graphene‐based electrochemical sensor for the detection of DA.     

α‐Propargyl amino acid‐derived optically active novel substituted polyacetylenes: Synthesis,secondary structures,and responsiveness to ions

Novel optically active substituted acetylenes HC? CCH₂CR¹(CO₂CH₃)NHR² [(S)‐/(R)‐ 1 : R¹ = H, R² = Boc, (S)‐ 2 : R¹ = CH₃, R² = Boc, (S)‐ 3 : R¹ = H, R² = Fmoc, (S)‐ 4 : R¹ = CH₃, R² = Fmoc (Boc = tert‐butoxycarbonyl, Fmoc = 9‐fluorenylmethoxycarbonyl)] were synthesized from α‐propargylglycine and α‐propargylalanine, and polymerized with a rhodium catalyst to provide the polymers with number‐average molecular weights of 2400–38,900 in good yields. Polarimetric, circular dichroism (CD), and UV–vis spectroscopic analyses indicated that poly[(S)‐ 1 ], poly[(R)‐ 1 ], and poly[(S)‐ 4 ] formed predominantly one‐handed helical structures both in polar and nonpolar solvents. Poly[(S)‐ 1a ] carrying unprotected carboxy groups was obtained by alkaline hydrolysis of poly[(S)‐ 1 ], and poly[(S)‐ 4b ] carrying unprotected amino groups was obtained by removal of Fmoc groups of poly[(S)‐ 4 ] using piperidine. Poly[(S)‐ 1a ] and poly[(S)‐ 4b ] also exhibited clear CD signals, which were different from those of the precursors, poly[(S)‐ 1 ] and poly[(S)‐ 4 ]. The solution‐state IR measurement revealed the presence of intramolecular hydrogen bonding between the carbamate groups of poly[(S)‐ 1 ] and poly[(S)‐ 1a ]. The plus CD signal of poly[(S)‐ 1a ] turned into minus one on addition of alkali hydroxides and tetrabutylammonium fluoride, accompanying the red‐shift of λ_max. The degree of λ_max shift became large as the size of cation of the additive. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Sensitivity Enhancement in Nickel Hydroxide/3D‐Graphene as Enzymeless Glucose Detection

A nickel hydroxide (Ni(OH)₂)/3D‐graphene composite is used as monolithic free‐standing electrode for enzymeless electrochemical detection of glucose. Ni(OH)₂ nanoflakes are synthesized by using a simple solution growth procedure on 3D‐graphene foam which was grown by chemical vapor deposition (CVD). The pore structure of 3D‐graphene allows easy access to glucose with high surface area, which leads to glucose detection with an ultrahigh sensitivity of 3.49 mA mM^?1 cm^?2 and a significant lower detection limit up to 24 nM. Cyclic voltammetry (CV) and potentionstatic mode is used for non‐enzymatic glucose sensing. The impedance and effective surface area have been studied well. The high sensitivity, low detection limit and simple configuration of Ni(OH)₂/three dimensional (3D)‐graphene composite electrodes can evoke its industrial application in glucose sensing devices.     

Metabolism of Deuterated Isomeric 6,7‐Dihydroxydodecanoic Acids in Saccharomyces cerevisiae – Diastereo‐ and Enantioselective Formation and Characterization of 5‐Hydroxydecano‐4‐lactone (=4,5‐Dihydro‐5‐(1‐hydroxyhexyl)furan‐2(3H)‐one) Isomers

The chemical synthesis of deuterated isomeric 6,7‐dihydroxydodecanoic acid methyl esters 1 and the subsequent metabolism of esters 1 and the corresponding acids 1a in liquid cultures of the yeast Saccharomyces cerevisiae was investigated. Incubation experiments with (6R,7R)‐ or (6S,7S)‐6,7‐dihydroxy(6,7‐²H₂)dodecanoic acid methyl ester ((6R,7R)‐ or (6S,7S)‐(6,7‐²H₂)‐ 1 , resp.) and (±)‐threo‐ or (±)‐erythro‐6,7‐dihydroxy(6,7‐²H₂)dodecanoic acid ((±)‐threo‐ or (±)‐erythro‐(6,7‐²H₂)‐ 1a , resp.) elucidated their metabolic pathway in yeast (Tables 1–3). The main products were isomeric ²H‐labeled 5‐hydroxydecano‐4‐lactones 2 . The absolute configuration of the four isomeric lactones 2 was assigned by chemical synthesis via Sharpless asymmetric dihydroxylation and chiral gas chromatography (Lipodex ^® E). The enantiomers of threo‐ 2 were separated without derivatization on Lipodex ^® E; in contrast, the enantiomers of erythro‐ 2 could be separated only after transformation to their 5‐O‐(trifluoroacetyl) derivatives. Biotransformation of the methyl ester (6R,7R)‐(6,7‐²H₂)‐ 1 led to (4R,5R)‐ and (4S,5R)‐(2,5‐²H₂)‐ 2 (ratio ca. 4 : 1; Table 2). Estimation of the label content and position of (4S,5R)‐(2,5‐²H₂)‐ 2 showed 95% label at C(5), 68% label at C(2), and no ²H at C(4) (Table 2). Therefore, oxidation and subsequent reduction with inversion at C(4) of 4,5‐dihydroxydecanoic acid and transfer of ²H from C(4) to C(2) is postulated. The 5‐hydroxydecano‐4‐lactones 2 are of biochemical importance: during the fermentation of Streptomyces griseus, (4S,5R)‐ 2 , known as L‐factor, occurs temporarily before the antibiotic production, and (?)‐muricatacin (=(4R,5R)‐5‐hydroxy‐heptadecano‐4‐lactone), a homologue of (4R,5R)‐ 2 , is an anticancer agent.     

A pair of diastereomeric 1:2 salts of (R)‐ and (S)‐2‐methylpiperazine with (2S,3S)‐tartaric acid

The crystal structures of a pair of diastereomeric 1:2 salts of (R)‐ and (S)‐2‐methylpiperazine with (2S,3S)‐tartaric acid, namely (R)‐2‐methylpiperazinediium bis[hydrogen (2S,3S)‐tartrate] monohydrate, (I), and (S)‐2‐methylpiperazinediium bis[hydrogen (2S,3S)‐tartrate] monohydrate, (II), both C₅H₁₄N₂²⁺·2C₄H₅O₆⁻·H₂O, each reveal the formation of well‐defined head‐to‐tail‐connected hydrogen tartrate chains; these chains are linked into a two‐dimensional sheet via intermolecular hydrogen bonds involving hydroxy groups and water molecules, resulting in a layer structure. The (R)‐2‐methylpiperazinediium ions lie between the hydrogen tartrate layers in the most stable equatorial conformation in (I), whereas in (II), these ions are in an unstable axial position inside the more interconnected layers and form a larger number of intermolecular hydrogen bonds than are observed in (I).     

N‐Heterocyclic Carbenes and Imidazole‐2‐thiones as Ligands for the Gold(I)‐Catalysed Hydroamination of Phenylacetylene

Gold(I) complexes of 1‐[1‐(2,6‐dimethylphenylimino)alkyl]‐3‐(mesityl)imidazol‐2‐ylidene (C^Imine_R), 1,3‐dimesitylimidazol‐2‐ylidene (IMes) and of the corresponding thione derivatives (S^Imine_R and IMesS) were prepared and structurally characterised. The solid‐state structure of the C^Imine_R and S^Imine_R gold(I) complexes showed monodentate coordination of the ligand and a dangling imine group that could bind reversibly to the metal centre to stabilise otherwise unstable catalytic intermediates. Interestingly, reaction of C^Imine_tBu with [AuCl(SMe₂)] led to the formation of [(C^Imine_tBu)AuCl], which rearranges upon crystallisation into the unusual complex cation [(C^Imine_tBu)₂Au]⁺, with AuCl₂^? as the counterion. The activity of the gold complexes in the hydroamination of phenylacetylene with substituted anilines was tested and compared to control catalyst systems. The best catalytic performance was obtained with [(C^Imine_tBu)AuCl], with the exclusive formation of the Markovnikov addition product in excellent yield (>95 %) regardless of the substituents on aniline.     

(2S,3S)‐2,6‐Dimethylheptane‐1,3‐diol,the oxygenated side chain of 22(S)‐hydroxycholestrol,and its synthetic precursor (R)‐4‐benzyl‐3‐[(2R,3S)‐3‐hydroxy‐2,6‐dimethylheptanoyl]‐1,3‐oxazolidin‐2‐one

(2S,3S)‐2,6‐Dimethylheptane‐1,3‐diol, C₉H₂₀O₂, (I), was synthesized from the ketone (R)‐4‐benzyl‐3‐[(2R,3S)‐3‐hydroxy‐2,6‐dimethylheptanoyl]‐1,3‐oxazolidin‐2‐one, C₁₉H₂₇NO₄, (II), containing C atoms of known chirality. In both structures, strong hydrogen bonds between the hydroxy groups form tape motifs. The contribution from weaker C—H...O hydrogen bonds is much more evident in the structure of (II), which furthermore contains an example of a direct short Osp³...Csp² contact that represents a usually unrecognized type of intermolecular interaction.     

Nanoporous Graphene with Single‐Atom Nickel Dopants: An Efficient and Stable Catalyst for Electrochemical Hydrogen Production

Single‐atom nickel dopants anchored to three‐dimensional nanoporous graphene can be used as catalysts of the hydrogen evolution reaction (HER) in acidic solutions. In contrast to conventional nickel‐based catalysts and graphene, this material shows superior HER catalysis with a low overpotential of approximately 50 mV and a Tafel slope of 45 mV dec^?1 in 0.5 M H₂SO₄ solution, together with excellent cycling stability. Experimental and theoretical investigations suggest that the unusual catalytic performance of this catalyst is due to sp–d orbital charge transfer between the Ni dopants and the surrounding carbon atoms. The resultant local structure with empty C–Ni hybrid orbitals is catalytically active and electrochemically stable.     

Surface analysis of plasma‐treated polydimethylsiloxane by x‐ray photoelectron spectroscopy and surface voltage decay

Surface states of polydimethylsiloxane (PDMS) treated by plasma were investigated by x‐ray photoelectron spectroscopy and surface voltage decay. X‐ray photoelectron spectroscopy confirmed the formation of a silica‐like (SiO_x, x = 3–4) oxidative surface layer. This layer increased in thickness with increasing exposure duration of plasma. Plasma exposure lowers the surface resistivity from 1.78 × 10¹⁴ to 1.09 × 10¹³ Ω □^?1 with increasing plasma treatment time. By measuring the decay time constant of surface voltage, the calculated surface resistivity was compared with the value measured directly by a voltage–current method; good agreement between the two methods was obtained. It was observed that plasma treatment led to a decrease in the thermal activation energy of the surface conduction from 31.0 kJ mol^?1 for an untreated specimen to 21.8 kJ mol^?1 for a plasma‐treated specimen for 1 h. Our results allow the examination of effects of plasma on the electrical properties of PDMS. Copyright © 2003 John Wiley & Sons, Ltd.     

Synthesis,Structures, and Light‐Induced Transformation of Keto‐Functionalized Selenidogermanate Complexes

A double‐decker (DD) type selenidogermanate complex with C=O functionalized organic decoration, [(R¹Ge₄)Se₆] ( 1 , R¹ = CMe₂CH₂COMe), was synthesized by reaction of R¹GeCl₃ with Na₂Se, and subsequently underwent a light‐induced transformation reaction to yield [Na(thf)₂][(RGe^IV)₂(RGe^III)(Ge^IIISe)Se₅] ( 2 ). Similar to the observations reported previously for the Sn/S homologue of 1 , the product comprises a mixed‐valence complex with a newly formed Ge–Ge bond. However, different from the transformation of the tin sulfide complex, the selenidogermanate precursor did not produce a paddle‐wheel‐like dimer of the DD type structure, but led to the formation of a noradamantane (NA) type architecture, which has so far been restricted to the Si/Se and Ge/Te elemental combination.     

1‐Aminoindan‐2‐ol,a Suitable Ligand for the Synthesis of Chiral,Intramolecularly Stabilized Compounds of Aluminum,Gallium, and Indium

The reactions of enantiomerically pure (1R, 2S)‐(+)‐cis‐1‐aminoindan‐2‐ol, (1S, 2R)‐(‐)‐cis‐1‐aminoindan‐2‐ol, and racemic trans‐1‐aminoindan‐2‐ol with trimethylaluminum, ‐gallium, and ‐indium produce the intramolecularly stabilized, enantiomerically pure dimethylmetal‐1‐amino‐2‐indanolates (1R, 2S)‐(+)‐cis‐Me₂AlO‐2‐C*HC₇H₆‐1‐C*HNH₂ ( 1 ), (1S, 2R)‐(‐)‐cis‐Me₂AlO‐2C*HC₇H₆‐1‐C*HNH₂ ( 2 ), (1R, 2S)‐(+)‐cis‐Me₂GaO‐2‐C*HC₇H₆‐1‐C*HNH₂ ( 3 ), (1R, 2S)‐(+)‐cis‐Me₂InO‐2‐C*HC₇H₆‐1‐C*HNH₂ ( 4 ), (1S, 2R)‐(‐)‐cis‐Me₂InO‐2‐C*HC₇H₆‐1‐C*HNH₂ ( 5 ), and racemic (+/‐)‐trans‐Me₂InO‐2‐C*HC₇H₆‐1‐C*HNH₂ ( 6 ). The compounds were characterized by ¹H NMR, ¹³C NMR, ²⁷Al NMR and mass spectra as well as 1 and 3 to 6 by determination of their crystal and molecular structures. The dynamic dissociation/association behavior of the coordinative metal‐nitrogen bond was studied by low temperature ¹H NMR spectroscopy.     

Curing kinetics,thermal, mechanical,and dielectric properties based on o‐cresol formaldehyde epoxy resin with polyhedral oligomeric (N‐aminoethyl‐γ‐amino propyl)silsesquioxane

The curing reaction and kinetics of o‐cresol formaldehyde epoxy resin (o‐CFER) with polyhedral oligomeric silsesquioxane of N‐aminoethyl‐γ‐amino propyl group (AEAP‐POSS) were investigated by differential scanning calorimetry (DSC). The thermal, mechanical, and dielectric properties of o‐CFER/AEAP‐POSS nanocomposites were investigated with thermogravimetric analysis (TGA), torsional braid analysis (TBA), tensile tester, impact tester, and electric analyzer, respectively. The results show that the activation energy (E) of curing reaction is 58.08 kJ/mol, and the curing reaction well followed the ?esták‐Berggren (S‐B) autocatalytic model. The glass transition temperature (T_g) increases with the increase in AEAP‐POSS content, and reaches the maximum, 107°C, when the molar ratio (N_s) of amino group to epoxy group is 0.5. The nanocomposites containing a higher percentage of AEAP‐POSS exhibited a higher thermostability. The AEAP‐POSS can effectively increase the mechanical properties of epoxy resin, and the tensile and impact strengths are 2.84 MPa and 143.25 kJ m^?2, respectively, when N_s is 0.5. The dielectric constant (ε), dielectric loss factor (tan δ), volume resistivity (ρ_v), and surface resistivity (ρ_s) are 4.98, 3.11 × 10^?4, 3.17 × 10¹² Ω cm³, and 1.41 × 10¹² Ω cm², respectively, similarly at N_s 0.5. Copyright © 2009 John Wiley & Sons, Ltd.     

Total Synthesis of (R,R,R)‐α‐Tocopherol Through Asymmetric Cu‐Catalyzed 1,4‐Addition

By introducing a disposable activating substituent at C‐3, the asymmetric 1,4‐addition to a notoriously unreactive 2‐substituted chromenone was achieved with high levels of (2R)‐stereoselectivity in the presence of a chiral Cu^I‐phosphoramidite complex as a catalyst. This paved the way for an efficient and conceptually novel synthesis of (R,R,R)‐α‐tocopherol from readily available starting materials.     

Helical polyacetylenes carrying 2,2,6,6‐tetramethyl‐1‐piperidinyloxy and 2,2,5,5‐tetramethyl‐1‐pyrrolidinyloxy moieties: Their synthesis,properties, and function

2,2,6,6‐Tetramethyl‐1‐piperidinyloxy (TEMPO)‐ and 2,2,5,5‐tetramethyl‐1‐pyrrolidinyloxy (PROXYL)‐containing (R)‐1‐methylpropargyl TEMPO‐4‐carboxylate ( 1 ), (R)‐1‐methylpropargyl PROXYL‐3‐carboxylate ( 2 ), (rac)‐1‐methylpropargyl PROXYL‐3‐carboxylate ( 3 ), (S)‐1‐propargylcarbamoylethyl TEMPO‐4‐carboxylate ( 4 ), and (S)‐1‐propargyloxycarbonylethyl TEMPO‐4‐carboxylate ( 5 ) (TEMPO, PROXYL) were polymerized to afford novel polymers containing the TEMPO and PROXYL radicals at high densities. Monomers 1–3 and 5 provided polymers with moderate number‐average molecular weights of 8200–140,900 in 49–97% yields in the presence of (nbd)Rh⁺[η⁶‐C₆H₅B^?(C₆H₅)₃], whereas 4 gave no polymer with this catalyst but gave polymers possessing low M_n (3800–7500) in 56–61% yield with [(nbd)RhCl]₂‐Et₃N. Poly( 1 ), poly( 2 ), and poly( 4 ) took a helical structure with predominantly one‐handed screw sense in THF and CHCl₃ as well as in film state. The helical structure of poly( 1 ) and poly( 2 ) was stable upon heating and addition of MeOH, whereas poly( 4 ) was responsive to heat and solvents. All of the free radical‐containing polymers displayed the reversible charge/discharge processes, whose capacities were in a range of 43.2–112 A h/kg. In particular, the capacities of poly( 2 )–poly( 5 )‐based cells reached about 90–100% of the theoretical values regardless of the secondary structure of the polymer, helix and random. Poly( 1 ), poly( 2 ), and poly( 4 ) taking a helical structure exhibited better capacity tolerance towards the increase of current density than nonhelical poly( 3 ) and poly( 5 ) did. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5431–5445, 2007