Emission from an excited triplet state during ECL

The application of Marcus theory of electron transfer reactions for the case of radical ion chemiluminescence of 9,10-diphenylanthracene (DPA) gives a high rate constant value (10⁹–10¹⁰ M^?1 s^?1) for the formation of the second triplet state (T₂). It is suggested that the near infrared emission observed during electrochemiluminescence of DPA is due to T₂ → T₁ fluorescence based on the high yield of T₂ (≈0.7) in the electron transfer reaction.     

Structure–property relationships for film‐forming copoly(amide imide)s

Thin films of copoly(amide imide)s (coPAIs) from dichloro‐dianhydride of trimellitimide‐N‐acetic acid and mixtures of diphenylmethane diamine (DPA) and cardo 9,9′‐bis‐phenylfluorene diamine (CDA) cast from solutions in dimethylacetamide (DMAA) were characterized by wide‐angle and small‐angle X‐ray scattering (WAXS and SAXS), dynamic mechanical thermal analysis (DMTA) (temperature interval: 293–703 K, frequency range: 1–100 Hz), and thermogravimetric analysis (TGA) (nitrogen flux, temperature interval: 303–973 K). The mean interchain spacings (WAXS) smoothly increased with the CDA/DPA molar ratio from 0.55 nm for CDA/DPA = 0/1 up to 0.60 nm for CDA/DPA = 1/0. The smooth patterns of the SAXS curves for all coPAIs were explained by the smearing‐out of electron density differences between densely‐packed and loosely‐packed microregions of coPAIs due to the wide dispersion of their sizes. The step‐like patterns of the TGA traces in the temperature intervals below and above 600 K were associated with successive weight losses due to the evaporation of residual water and of DMAA, and to the thermal degradation of diamine and dianhydride chain fragments, respectively. As could be inferred from the TGA data, the loosely‐packed regions comprise about 25–35% of the total volume of studied coPAIs. The mechanical relaxations observed in all coPAIs at T_β < T_α′ < T_α (DMA) were attributed to the onset of non‐cooperative segment motion in loosely‐packed regions, of cooperative segment motion in loosely‐packed regions, and of cooperative segment motion in densely‐packed regions, respectively. At constant frequency, the sub‐glass relaxations were roughly composition‐independent, while chain‐stiffening effect was assumed to be responsible for the smooth increase of T_α′ and T_α, as well as of the corresponding apparent activation energies with the CDA/DPA ratio. Copyright © 2003 John Wiley & Sons, Ltd.     

ESR study of the photo-induced decomposition of polypropylene in the presence of N,N,N′,N′-tetramethyl-p-phenylenediamine

The mechanism of uv (λ > 325 nm) photodegradation of polypropylene (PP) containing N,N,N′,N′-tetramethyl-p-phenylenediamine (T₄MPD) has been investigated by means of ESR spectroscopy. The observed spectra after uv irradiation of both isotactic-PP (IPP) and stereoblock-PP (SPP) samples in vacuum at 77 K consisted principally of a broad singlet which was assigned to a T₄MPD cation radical (T₄MPD^+·). On the other hand, the spectrum observed after irradiation of an atactic polypropylene (APP) sample at 77 K in vacuum was resolved into several components which decayed almost up to ca. 263 K to give rise to the broad singlet of T₄MPD^+·. One component was a sharp quartet which was assigned to a methyl radical, ·CH₃·. The other component, a singlet, was attributed to a trapped electron, e_t^?.By comparison of the ESR spectrum of deuterated T₄MPD with that of the normal compound it was found that 60 ～ 70% of the methyl radicals arose from the added T₄MPD due to β-scission, which also formed the N,N,N′-trimethyl-p-phenylenediamine radical, T₃MPD·. The T₃MPD· radical presumably captures an electron at lower temperatures to become a carbanion, T₃MPD^?, which releases the electron to reproduce the T₃MPD· radical at elevated temperatures. This production of the radical T₃MPD· due to the liberation of an electron provides an explanation for the observed increase in intensity of the decay curve in the temperature range from ? 168 K to 185 K. The remaining fraction, 30 ～ 40%, of the total methyl radicals was produced from the PP matrix by an energy transfer from the excited T₄MPD¹ to the PP matrix. The broad singlet which appeared in the temperature range near 195 K was attributed to an acyl radical ～CH₂CH(CH₃)CH₂?O from the observed g-value. By photoillumination of this sample this broad singlet was converted reversibly into the quartet which was assigned to the radical ～CH₂CH(CH₂·)CH₂CHO.     

Interface-Anchored Covalent Organic Frameworks@Amino-Modified Ti3C2Tx MXene on Nylon 6 Film for High-Performance Deformable Supercapacitors

Designing deformable supercapacitors (D-SCs) that have robust skeleton and smoothly active channels for charges kinetic migration and faradic storage are highly crucial for wearable systems. Here, we develop the high-performance D-SCs made of the covalent organic frameworks(COF)@amino-modified Ti₃C₂T_x deposited on decorated nylon 6 (DPA) film (COF@N-Ti₃C₂T_x/DPA) via layer-by-layer fabrication. The hierarchical COF@N-Ti₃C₂T_x/DPA exhibits admirable specific capacitance, rate performance and cycling stability in three-electrode system due to the superior H⁺ storage property and large interfacial charge transfer clarified by density functional theory calculations. Additionally, the solid-state D-SCs deliver favourable energy density and practical energy-supply applications. Particularly, the solid-state D-SCs present high deformable stabilities, with regard to 80.7, 80.6 and 83.4 % capacitance retention after 5000 bending cycles, 2000 stretching cycles and 5000 folding cycles, separately.     

The chemical effect of furfuryl amide on the enhanced performance of the diphenolic acid derived bio-polybenzoxazine resin

As a renewable chemical, diphenolic acid (DPA) has attracted immense interest in bio-based polymer science. However, its application for polybenzoxazines is limited due to decarboxylation, that is, the release of CO₂ during the curing reaction of benzoxazine. In this study, the amidation strategy of converting DPA to diphenolic amides (DPAM) was demonstrated to solve this problem while simultaneously improving the thermal properties of polybenzoxazine. DPA was amidated by separately using four amines (hexamine, cyclohexylamine, furfurylamine, and aniline), then reacted with furfurylamine and paraformaldehyde to synthesize their benzoxazine monomers. By using TGA and DMA, all amide-containing polybenzoxazines were found to exhibit excellent thermal stabilities. Among all of the benzoxazine resins, poly(DFA-fa), which was obtained from amidation with furfurylamine, exhibited the highest glass transition temperature (T_g) of 310°C and a decomposition temperature (T_d10) of 406°C. Furthermore, a possible post-curing reaction mechanism was proposed to explain the outstanding thermal performance of poly(DFA-fa) resin. This study proposes an innovative strategy to solve the decarboxylation of DPA-based polymers, which is of significance for high-performance bio-based polymers.     

The construction of a two-dimensional organic–inorganic hybrid double perovskite ferroelastic with a high Tc and narrow band gap

Two-dimensional (2D) hybrid double perovskites have attracted extensive research interest for their fascinating physical properties, such as ferroelectricity, X-ray detection, light response and so on. In addition, ferroelastics, as an important branch of ferroic materials, exhibits wide prospects in mechanical switches, shape memory and templating electronic nanostructures. Here, we designed a 2D phase-transition double perovskite ferroelastic through a structurally progressive strategy. This evolution is core to our construction process from 0D to 1D and AgBi-based 2D. In this way, we successfully synthesized 2D lead-free ferroelastic (DPA)₄AgBiBr₈ (DPA = 2,2-dimethylpropan-1-aminium) with a high Curie temperature (T_c), which shows a narrower band gap than 0D (DPA)₄Bi₂Br₁₀ and 1D (DPA)₅Pb₂Br₉. Moreover, the mechanism of structural phase transition and molecular motion are fully characterized by temperature dependent solid-state NMR and single crystal XRD. (DPA)₄AgBiBr₈ injects power into the discovery of new ferroelastics or the construction and dimensional adjustment in new hybrid double perovskites.

By using a lead-free AgBi-based scheme, we successfully synthesized a two-dimensional double perovskite ferroelastic (DPA)₄AgBiBr₈ with high T_c of 375 K and a narrow band gap of 2.44 eV, where DPA is 2,2-dimethylpropan-1-aminium.     

Silole‐containing poly(diphenylacetylene): Synthesis,characterization, and light emission

A disubstituted polyacetylene consisting of a poly(diphenylacetylene) backbone and a 1,2,3,4,5‐pentaphenylsilole (SiC₄Ph₅) pendant, that is, ? {(C₆H₅) C?C [C₆H₄O(CH₂)₃C?CSiC₄Ph₅]}_n? (PS3DPA), was synthesized, and its light emission from both the backbone and the pendant was evaluated. The polymerization of C₆H₅C?CC₆H₄O(CH₂)₃C?CSiC₄Ph₅ with two ethynyl groups was effected with WCl₆–Ph₄Sn as the catalyst. The structure and properties of PS3DPA were characterized and evaluated by IR, UV, NMR, thermogravimetric analysis, differential scanning calorimetry, photoluminescence, and electroluminescence analyses. The ethynyl group of the diphenylacetylene moiety was polymerized exclusively, giving a soluble PS3DPA. The chloroform solution of PS3DPA showed a backbone emission that peaked at 522 nm, whereas the silole pendant was nonradiative at room temperature. The polymer did not show the aggregation‐induced emission phenomenon, probably because the silole clusters were difficult to form when the polymer chains aggregated because of the very high rigidity of the main chain. Intramolecular rotations of the phenyl groups of the silole moieties were responsible for the nonradiative decay of the silole chromophore. The intramolecular rotations, however, could be largely restricted in a cooling process of the polymer solution, showing cooling‐enhanced emission. The silole emission became dominant at lower temperatures. A multilayer electroluminescence device based on PS3DPA emitted a green light that peaked at 512 nm. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2487–2498, 2006     

Spatially resolved emission using a geometry-dependent system function and its application to excitation temperature profile measurement

As typical emission spectroscopy involves chord integration along the line of sight, a local measurement with high spatial resolution is attempted using simple lens optics in this work. In the experiment, chord integrated optical plasma emission profile was measured by moving a scanning lens located outside the plasma. The measured emission intensities were spatially reconstructed by employing a geometry-dependent system function, and the local (i.e., only from the lens focal point) emission intensities were obtained with all out-focused emissions subtracted. The 34 different Ar I emission lines spatially reconstructed in this way were used to determine excitation temperature (T_exc) of the argon plasma by the Boltzmann plot method. Being different from the plasma driven at 13.56 MHz where a rather uniform profile was obtained, the spatial profile of T_exc from the plasma driven at 90 MHz showed a hollow profile, which is similar to that of the electron temperature (T_e) measured by a Langmuir probe. This hollow profile is attributed from the electromagnetic phenomena such as skin effect and standing wave effect. The similar spatial tendency of T_exc and T_e implies that T_exc can be a representative of T_e. This is particularly useful for the cases in which conventional Langmuir probe measurements are limited, such as in large size plasmas.     

Flame Emission Spectra in the Region 400–600 nm during Low-Pressure Silane and Dichlorosilane Oxidation

The flame emission in the region 400–600 nm during monosilane and dichlorosilane oxidation (initial pressures of 3–20 torr; T = 300 K) is caused by radical luminescence processes on the surface of aerosol microparticles of the SiO₂ formed. The generation of energy by the interaction of gas-phase species with the SiO₂ surface at the initial stages of the phase formation depends on the presence of the intrinsic structural defects Si⁺ and defects like Si⁺ implanted into SiO₂. The addition of SF₆ to the starting mixture results in the appearance of emission bands due to the Si⁺ defects in the radical luminescence spectrum.     

Electrogenerated chemiluminescence. XXIV. Electrochemistry and electrogenerated chemiluminescence of 9,10-dichloro-9,10-dihydro-9,10-diphenylanthracene

A study of the electrochemistry and electrogenerated chemiluminescence (e.c.l.) of 9,10-dichloro-9,10-dihydro-9,10-diphenylanthracene (DPACl₂) in acetonitrile solutions using rotating ring—disk electrode and stationary electrode techniques is described. The measured e.c.l. efficiency was about 0.1 to 0.8%, smaller than that observed for the corresponding DPA radical ion annihilation e.c.l. The emission is independent of applied external magnetic field, supporting the mechanism involving direct formation of emitting singlet. The e.c.l. emission and the electroreduction of DPACl₂ depend on the chloride concentration in the solution; the results suggest that this dependence is an electrode surface effect.     

Synthesis and characterization of an MRI Gd‐based probe designed to target the translocator protein

DPA‐713 is the lead compound of a recently reported pyrazolo[1,5‐a]pyrimidineacetamide series, targeting the translocator protein (TSPO 18 kDa), and as such, this structure, as well as closely related derivatives, have been already successfully used as positron emission tomography radioligands. On the basis of the pharmacological core of this ligands series, a new magnetic resonance imaging probe, coded DPA‐C₆‐(Gd)DOTAMA was designed and successfully synthesized in six steps and 13% overall yield from DPA‐713. The Gd‐DOTA monoamide cage (DOTA = 1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid) represents the magnetic resonance imaging reporter, which is spaced from the phenylpyrazolo[1,5‐a]pyrimidineacetamide moiety (DPA‐713 motif) by a six carbon‐atom chain. DPA‐C₆‐(Gd)DOTAMA relaxometric characterization showed the typical behavior of a small‐sized molecule (relaxivity value: 6.02 mM^?1 s^?1 at 20 MHz). The good hydrophilicity of the metal chelate makes DPA‐C₆‐(Gd)DOTAMA soluble in water, affecting thus its biodistribution with respect to the parent lipophilic DPA‐713 molecule. For this reason, it was deemed of interest to load the probe to a large carrier in order to increase its residence lifetime in blood. Whereas DPA‐C₆‐(Gd)DOTAMA binds to serum albumin with a low affinity constant, it can be entrapped into liposomes (both in the membrane and in the inner aqueous cavity). The stability of the supramolecular adduct formed by the Gd‐complex and liposomes was assessed by a competition test with albumin. Copyright © 2013 John Wiley & Sons, Ltd.     

Spectral and photochemical properties of aromatic nitrenes

Absorption and emission spectra of para-substituted phenyl nitrenes have been studied in glassy ethanol at 77 K. Absorption spectra of nitrenes with neutral and donor substituents are similar to benzyl radical absorption and show three bands at 400–450, 320 and 250 nm. The emission is assigned to T₁-T₀ fluorescence. Nitrenes could be photoreduced to substituted anilines at 77 K.     

A picosecond transient absorption study of the intramolecular excited state proton transfer in 3-hydroxyflavone: assignment of the observed bands

The time-resolved transient absorption and gain of 3-hydroxyflavone in ethanol ( T = 300 and 173 K) and MCH ( T = 300 and 198 K) has been investigated. Two absorption bands (A and B) and two gain bands (E₁ and E₂) have been observed. Band A (lying in the 5200 Å spectral region) appears during and just after the excitation step and is assigned to the normal excited form N_x Band B (lying in the 6050 Å spectral region) appears after band A and is assigned to the tautomer form T. A gain band E₂ (lying at λ=5400 Å) appears at the same time as the B band and is attributed to the T→T emission. A gain band E₁ (lying at λ = 5730 Å) appears earlier than the E₂ band. Its origin is discussed and two possible assignments are presented: vibronic progression of the emission spectrum of T or formation of an intermediate species on the proton transfer pathway from N_x to T.     

Pulse radiolysis studies of poly(methyl methacrylate) containing pyrene

A pulse radiolysis study of poly(methyl methacrylate) in the presence of pyrene has been carried out in the temperature range 100–295 K. The concentration of pyrene was changed from 10⁻³ to 10⁻¹ mol dm⁻³. The absorption/emission spectra and kinetics of solute excited states and solute radical ions were investigated. It was found that pyrene excited states were formed as a result of their radical ion recombination in a time scale up to seconds. The decay of solute radical ions was influenced by photobleaching and can be described by a time-dependent rate constant. The activation energy of Py ions decay was temperature dependent and was equal to 35.7 and 1.2 kJ/mol for temperatures >T_γ and <T_γ, respectively, where T_γ ∼ 175 K represented the transition temperature responsible for γ-relaxation. The reaction mechanism was proposed. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1209–1215, 1998     

Electron spin emission spectra from pairs of radicals

Electron spin emission from both radicals of a pair has been observed. It is demonstrated that it is possible to explain the polarization by the radical pair mechanism if nuclear relaxation is fast enough. The extent of ST_?1 mixing induced by an anisotropic g-factor is deduced.     

The Role of Ligand Topology in the Decomplexation of Luminescent Lanthanide Complexes by Dipicolinic Acid

In this study, we present the aqueous solution behavior of two luminescent lanthanide antenna complexes (Eu³⁺? 1 , Dy³⁺? 9 ) with different ligand topologies in the presence of dipicolinic acid (DPA, pyridine‐2,6‐dicarboxylic acid). Macrocyclic (1,4,7,10‐tetraazacyclododecane‐1,4,7‐triacetic acid, DO3A, 9 ) and acyclic (1,4,7‐triazaheptane‐1,1,7,7‐tetraacetic acid, DTTA, 1 ) ligands have been selected to form a ratiometric pair in which Dy³⁺? 9 acts as a reference and Eu³⁺? 1 acts as a probe for the recognition of DPA. The pair of luminescent complexes in water reveals the capability to work as a DPA luminescent sensor. The change of emission intensity of Eu³⁺ indicates the occurrence of a new sensitization path for the lanthanide cation through excitation of DPA. NMR evidence implies the presence of free 1 and mass spectrometry shows the formation of emitting [EuDPA₂]^? as a result of a ligand exchange reaction.     

Radical-Enhanced Intersystem Crossing in Perylene-Oxoverdazyl Radical Dyads

Attaching stable radicals to organic chromophores is an effective method to enhance the intersystem crossing (ISC) of the chromophores. Herein we prepared perylene-oxoverdazyl dyads either by directly connecting the two units or using an intervening phenyl spacer. We investigated the effect of the radical on the photophysical properties of perylene and observed strong fluorescence quenching due to radical enhanced ISC (REISC). Compared with a previously reported perylene-fused nitroxide radical compound (triplet lifetime, τ_T=0.1 μs), these new adducts show a longer-lived triplet excited state (τ_T=9.5 μs). Based on the singlet oxygen quantum yield (Φ_Δ=7 %) and study of the triplet state, we propose that the radical enhanced internal conversion also plays a role in the relaxation of the excited state. Femtosecond fluorescence up-conversion indicates a fast decay of the excited state (<1.0 ps), suggesting a strong spin-spin exchange interaction between the two units. Femtosecond transient absorption (fs-TA) spectra confirmed direct triplet state population (within 0.5 ps). Interestingly, by fs-TA spectra, we observed the interconversion of the two states (D₁↔Q₁) at ∼80 ps time scale. Time-resolved electron paramagnetic resonance (TREPR) spectral study confirmed the formation of the quartet sate. We observed triplet and quartet states simultaneously with weights of 0.7 and 0.3, respectively. This is attributed to two different conformations of the molecule at excited state. DFT computations showed that the interaction between the radical and the chromophore is ferromagnetic (J>0, 0.05∼0.10 eV).     

Thermodynamic quantities for the different steps involved in the mechanism of osmium(VIII) catalysed oxidation of l-lysine by a new oxidant,diperiodatoargentate(III) (stopped flow technique)

The kinetics of Os(VIII) catalysed oxidation of l-lysine by diperiodatoargentate(III) (DPA) in alkaline medium at T = 298 K and a constant ionic strength of 0.50 mol · dm^?3 was studied spectrophotometrically. The oxidation products are aldehyde (5-aminopentanal) and Ag(I). The stoichiometry is i.e. [l-lysine]:[DPA] = 1:1. The reaction is of first order in [Os(VIII)] and [DPA] and is less than unit order in both [l-lys] and [alkali]. Addition of periodate has no effect on the reaction. Effect of added products, ionic strength, and dielectric constant of the reaction medium have been investigated. The oxidation reaction in alkaline medium has been shown to proceed via a Os(VIII)-l-lysine complex, which further reacts with one molecule of deprotonated DPA in a rate determining step followed by other fast steps to give the products. The main products were identified by spot test, IR, and GC-MS. The reaction constants involved in the different steps of the mechanism are calculated at different temperatures. The catalytic constant (K_C) was also calculated at different temperatures. From the plots of lg K_C versus 1/T, values of activation parameters with respect to the catalyst have been evaluated. The activation parameters with respect to slow step of the mechanism are computed and discussed and thermodynamic quantities are also determined. The active species of catalyst and oxidant have been identified.     

Model for measuring excitation temperatures on a relative basis without transition probabilities

A variation of the conventional slope or two-line method is proposed for determining excitation temperature (T_exc) by atomic emission. T_exc is measured relative to some known reference value, which can be derived either from the emission source itself or from some reference line source of known temperature. Measurement of T_exc with a relative error of 1–10% should be possible for reasonable experimental uncertainties in T_ref and the measured line intensities. The proposed method is useful for some interesting and important experiments with emission lines for which the transition probabilities are either unknown or of questionable accuracy. Such experiments include measuring the dependence of T_exc on observation position or operating parameters, determining whether or not different emitting species have the same T_exc, and identifying possible deviations from a Boltzmann distribution of excited state populations within a particular emitting species.     

Energy ordering of the B and C states in XeCl,XeBr, and KrCl,from temperature dependence of emission spectra

Inert-gas halide emission spectra from a Tesla discharge are studied as a function of pressure and temperature. From the temperature dependence of the infinite pressure ratio of broad-band (C → A and B → A) emission to B → X emission, the energy separations, T_eC - T_eB, are found to be ?130 cm^?1 (XeCl), ?80 cm^?1 (XeBr) and 375 cm^?1 (KrCl). Estimates of the (C → A)/(B → X) spontaneous emission branching ratios agree well with theoretical predictions.