Photochromism of dihydroindolizines Part XIX. Efficient one‐pot solid‐state synthesis,kinetic, and computational studies based on dihydroindolizine photochromes

For the first time, one‐pot solid‐state synthesis of 12 photochromic materials based on photochromic dihydroindolizine system substituted in both fluorene part (region A) and the heterocyclic part (region C) has been established. This method has immense advantages, which are short‐time reaction, high‐yield and low‐yield by‐products, and easily purification and separation processes. In addition, this method will help in getting over the tremendously purification and low‐yield problems faced since the worth‐finding of this family of photochromic materials. The absorption maxima (λ_max) and the half‐lives (t_1/2) of the colored betaines were detected in all cases using multichannel UV/Vis spectrophotometric measurements. The rate constants of the thermal back reaction of the betaines were determined at constant temperature by measuring the decrease in the maximum absorption intensity (λ_max) with time. The half‐lives (t_1/2) and rate constants (k) of betaines under examination were calculated by plotting lnA against time (t). The kinetic measurements could be detected by both spectra scan and time‐dependent decay measurements. Examination of the Arrhenius parameters reveals an underlying compensation between E_a and log A, whereby an increase in E_a is opposed by an increase in log A. The compensation appears in the corresponding Eyring parameters, ΔH^≠ and ΔS^≠; betaine structural changes that lead to lower, more favorable enthalpies of activation engender opposing entropic changes. At the isokinetic temperature T_iso = β, structural changes do not affect the rate constant of a reaction series because the changes of ΔH^≠ are counterbalanced by changes of ΔS^≠. The existence of an isokinetic relationship indicates a common structure of the transition state of all thermal back reaction of betaine under investigation. The computational results suggest that the decoloration reaction is a two‐step mechanism. The first step corresponds to the transoid–cisoid isomerization with an activation barrier of 10.3 kJ mol^?1, and the second step is the ring closure from the cisoid intermediate with a barrier 71.3 kJ mol^?1, which represent the rate determining step for thermal decoloration. The photochemical ring opening of DHIs to betaines is a disrotatory 1,5‐electrocyclic reaction, whereas the thermal ring‐closing occurs in the conrotatory mode. Copyright © 2016 John Wiley & Sons, Ltd.     

Effect of substituents in phenol and aniline nucleophiles on activation parameters in SNAr reactions

Changes of activation parameters, ΔH^≠ and ΔS^≠, with σ constants of substituents in the phenol and aniline nucleophiles for their S_NAr reactions in various solvents give the δΔH^≠ and δΔS^≠ reaction constants which are linearly related. The dependence obtained, δΔH^≠ versus δΔS^≠, allow estimation of the contribution of changes of the internal enthalpy, δΔH^≠_int, to the enthalpy reaction constant, δΔH^≠, which give a linear dependence on the Hammett reaction constants, ρ. The results obtained show that the substituent effects on the charge development in the transition state (TS) are governed by the magnitude of δΔH^≠_int. Copyright © 2009 John Wiley & Sons, Ltd.     

Kinetics and related studies of the formation of 2,3‐dihydroquinazolin‐4(1H)‐ones in the presence of different benzaldehyde derivatives

The kinetics and activation parameters for the reaction between 2‐amino‐benzamide and some benzaldehyde derivatives in the presence of formic acid have been reported and discussed. A linear plot of lnk vs l/T showed that the reactions obey the Arrhenius equation. Both the Arrhenius and the Eyring equations were used to calculate the activation energy. The effect of nitro groups was studied on different positions of benzaldehyde. For all substituents, the reactions followed second‐order kinetics, and the partial orders of reactions were recognized with respect to each reactant. Comparisons between the magnitudes of ΔH^? and TΔS^?showed that the reactions were enthalpy controlled. The validity of the isokinetic relationship and the compensation effect was tested, and the isokinetic temperature (β) was obtained. A linear enthalpy‐entropy plot (ΔH^?versusΔS^?) showed that the compensation effect is established, and this process occurs via a same mechanism across a series of reactions. From the Van't Hoff and Exner's plots, the isokinetic temperature was obtained.     

Towards mechanisms of bimolecular nucleophilic reactions in solution—probing the variation of the activation parameters in the reactions of aromatic compounds

Variation of the activation parameters in the S_N2, acyl‐transfer, S_NAr, S_NV, and Ad_N reactions offers a uniquely useful probe for the mechanistic features of these reactions in solution. New approach uses the substituent effects on the aromatic ring to the variation of the activation parameters, ΔH^≠ and ΔS^≠, in the above reactions in the frameworks of the Hammett‐like equations in order to evaluate the resultant δΔH^≠ and δΔS^≠ reaction constants. Compensation relationships of δΔH^≠ versus δΔS^≠ allow one to estimate the contribution of changes of the internal enthalpy, δΔH^≠_int, to the enthalpy reaction constant, δΔH^≠, that is inherent to bimolecular nucleophilic reactions and gives a single linear dependence on the Hammett ρ reaction constants for these reactions. The deviations from dependence of δΔH^≠_int versus ρ serve as useful points of interpretation of changes of the transition state structure or reaction mechanism. The results obtained show that the substituent effects in the substrates, nucleophiles, and leaving groups on the mechanistic features in bimolecular nucleophilic reactions are governed by the magnitude of δΔH^≠_int. Copyright © 2011 John Wiley & Sons, Ltd.     

Reactivity of sodium arenesulfinates in the substitution reaction to γ‐functionalized allyl bromides

The kinetics of nucleophilic bimolecular substitution reactions of γ‐functionalized allyl bromides with non‐substituted and p‐substituted sodium arenesulfinates has been studied. Both the structure of allyl bromides and nucleophilicity of arenesulfinate ions exerted a significant effect on the values of the kinetic parameters such as the second‐order rate constants k, activation energy E_A, and changes in the entropy ΔS^≠, enthalpy ΔH^≠, and free energy ΔG^≠ of the formation of the activated complex from reactants. Based on the evaluation of kinetic parameters, the reactants could be arranged, according to their decreasing reactivity in the S_N2‐reactions as follows: p‐toluenesulfinate ion > benzenesulfinate ion > p‐chlorobenzenesulfinate ion and 4‐bromo‐2‐butenenitrile > 1,3‐ dibromopropene, respectively. Comparison was also made between the kinetic data obtained and some delocalization reactivity indexes for both the substrates and nucleophiles. The enthalpy–entropy compensation effect was observed for the reactions of sodium arenesulfinates with γ‐functionalized allyl bromides. Copyright © 2009 John Wiley & Sons, Ltd.     

Selectivity of nitro versus fluoro substitution in arenes in their reactions with charged O‐ and S‐nucleophiles

The relative mobility of nitro and fluoro substituents in 1,3‐dinitro‐ and 1‐fluoro‐3‐nitrobenzenes, 3,5‐dinitro‐ and 3‐fluoro‐5‐nitrobenzotrifluorides under the action of the nucleophiles (2ArYH)·K₂CO₃ and ArY^?K⁺ in solution and the nucleophiles ArYH·K₂CO₃ (Y = O, S) under heterogeneous conditions was studied by a competitive method in DMF at 40–140 °C. The unique dependences of ΔΔH^≠ on ΔΔS^≠ and ΔΔH^≠ on ΔΔG^≠ were determined for all the substrates and nucleophiles. The dependence of the mechanistic pathway on the nucleophile is discussed. Two results are relevant to the reactions studied: (i) substituent effects in the nucleophiles (2ArYH)·K₂CO₃ and ArYH·K₂CO₃ on the activation entropies suggest that the entropy favours the displacement of nitro group; (ii) the negative signs of ΔΔH^≠ and ΔΔS^≠ for the reactions of the nucleophiles ArY^?K⁺ indicate that the enthalpy determines the displacement of nitro group. It is concluded that the selectivity of the reactions with aryloxide and arylthioxide ions cannot be explained by the hard–soft acid–base principle only. Copyright © 2007 John Wiley & Sons, Ltd.     

Dynamic 1H NMR investigation along with a theoretical study around the C–C and C = C bonds in a particular phosphorus ylide

In the present work, the dynamic ¹H NMR effects were investigated at variable temperatures within a particular phosphorus ylide involving a 2‐benzoxazolinone around the carbon–carbon single bond and also partial carbon–carbon double bond in two Z‐ and E‐rotational isomers. Activation and kinetic parameters including ΔH^≠, ΔG^≠, ΔS^≠ and E_a were determined in accord with the dynamic ¹H NMR data for three rotational processes. In addition, theoretical studies based upon rotation around the same bonds were investigated using ab initio and DFT methods at the HF/6‐31G(d,p) and B3LYP/6‐31G(d,p) levels of theory. Theoretical activation and kinetic parameters including ΔH^≠, ΔG^≠, ΔS^≠ and E_a were calculated at 298 K and experimental temperatures for five rotational processes. These results (experimental and theoretical), taken together, indicate that the rotational energy barrier around the C = C double bond was considerably high and the observation of the two rotational isomers was impossible (seen as a single isomer) at the high temperatures, in this case rotation around the C = C bond was too fast on the NMR time scale. When the temperature was relatively low, the rate of rotation was sufficiently slow; therefore, observation of the two Z‐ and E‐isomers was possible. In addition, calculations at the HF/6‐31G(d,p) level of theory showed very favorable results in agreement with the experimental data on rotation around the C = C bond. While, B3LYP level using the 6‐31G(d,p) basis set was provided the reasonable data for the restricted rotations around the C–C and C–N single bond. Copyright © 2012 John Wiley & Sons, Ltd.     

The number of independent traces and supertraces on symplectic reflection algebras

It is shown that A:= H₁, _η (G), the sympectic reflection algebra over ?, has T_G independent traces, where T_G is the number of conjugacy classes of elements without eigenvalue 1 belonging to the finite group G ? Sp(2N) ? End(?^2N) generated by the system of symplectic reflections.

Simultaneously, we show that the algebra A, considered as a superalgebra with a natural parity, has S_G independent supertraces, where S_G is the number of conjugacy classes of elements without eigenvalue -1 belonging to G.

We consider also A as a Lie algebra A^L and as a Lie superalgebra A^S.

It is shown that if A is a simple associative algebra, then the supercommutant [A^S, A^S] is a simple Lie superalgebra having at least S_G independent supersymmetric invariant non-degenerate bilinear forms, and the quotient [A^L, A^L]/([A^L, A^L] ∩ ?) is a simple Lie algebra having at least T_G independent symmetric invariant non-degenerate bilinear forms.     

Effects of substituents on activation parameters in SN2 reactions at aliphatic carbon in solution

Changes of the activation parameters in aliphatic S_N2 reactions with anionic and neutral nucleophiles in various solvents, ΔH^≠ and ΔS^≠, were correlated with σ constants of the substituents. The resultant δΔH^≠ and δΔS^≠ reaction constants are linearly related for variations of substituents at the substrate, leaving group and nucleophile. Correlations of δΔH^≠ versus δΔS^≠ allow the estimation of the contribution of changes of the internal enthalpy, δΔH, to the enthalpy reaction constant, δΔH^≠, which gives a single linear dependence on the Hammett ρ reaction constants. The deviations from the dependence of δΔH versus ρ can be interpreted in terms of changes in the transition state structure in S_N2 reactions. The results obtained show that the substituent effects on the charge development in the transition state are governed by the magnitude of δΔH. Copyright © 2009 John Wiley & Sons, Ltd.     

Resistive sensor of weak magnetic fields on the basis of a thick HTSC film

The following parameters have been obtained for a thick (thickness t ～50 μm) film of high-temperature superconducting ceramics of the Bi-2223 system have been implemented: magnetosensitivity S _u ～ 29 V T^?1 and resolutions δB ～ 3 nT and δ? ～ 4?₀ in magnetic field and magnetic flux, respectively. It is shown that the film magnetosensitivity can be significantly increased due to the size effect. The expected characteristics, estimated with allowance for the size effect, are S _u ≥ 1000 V T^?1, δB ～ 0.01 nT, δ? ～ 0.01 ?₀, and the range of dynamic measurement ≥150 dB.     

NMR investigations of molecular motions inp-n-hexyloxybenzylidene-p′-n-propylaniline

Proton spin-lattice relaxation times,T ₁, have been measured in the smectic phases, S _G ² , S _G ¹ and S_A, and in the nematic phase of HxBPA, in the temperature range, 220K<T<360 K. In the S _G ¹ and S _G ² phases,T ₁ has been measured at 15 and 40 MHz. The (S _G ¹ →S _G ² ) and (S _G ² →S _G ¹ ) transitions are clearly seen as discontinuities inT ₁. The former transition is seen to be due to possible freezing or change of hydrocarbon chain motions of the molecule. Our data in the S _G ¹ phase have been fitted to a model in which anisotropic rotational diffusion of the end hydrocarbon chains as also that of the rigid part of the molecule are considered. In the nematic phase, at 351 K, the observed behaviour ofT ₁, measured in the frequency range, 5 to 40 MHz, agrees well with the theoretical predictions of Uklejaet al and Freed, who take into account long range collective order fluctuations and local reorientations. Using these theories, the correlation time for short range reorientations has been calculated from our results to be 4.3 × 10⁻¹⁰ and 1.1 × 10⁻⁹ s respectively.     

Propanolysis of arenesulfonyl chlorides: Nucleophilic substitution at sulfonyl sulfur

We have studied the mechanism of solvolysis of arenesulfonyl chlorides by propan‐1‐ol and propan‐2‐ol at 303‐323 K. Kinetic profiles were appropriately fit by first‐order kinetics. Reactivity increases with electron‐donating substituents. Ortho‐alkyl substituted derivatives of arenesulfonyl chlorides show increased reactivity, but the origin of this “positive” ortho‐effect remains unclear. Likely, ortho‐methyl groups restrict rotation around the C‐S bond, facilitating the attack of the nucleophile. No relevant reactivity changes have been found with propan‐1‐ol and propan‐2‐ol in terms of nucleophile steric effect. The existence of isokinetic relationships for all substrates suggests a single mechanism for the series. Solvolysis reactions of all substrates in both alcohols show isokinetic temperatures (T_iso) close to the working temperature range, which is an evidence of the process being influenced by secondary reactivity factors, likely of steric nature in the TS. Solvation plays a relevant role in this reaction, modulating the reactivity. In some cases, the presence of t‐Bu instead of Me in para‐ position leads to changes in the first solvation shell, increasing the energy of the reaction (ca. 1 kJ·mol^?1). The obtained results suggest the same kinetic mechanism of solvolysis of arenesulfonyl chlorides for propan‐1‐ol and propan‐2‐ol, as in MeOH and EtOH, where bimolecular nucleophilic substitution (S_N2) takes place with nucleophilic solvent assistance of one alcohol molecule and the participation of the solvent network involving solvent molecules of the first solvation shell.     

Temperature dependence of the lattice parameters in the S1G and S2G phases of HxBPA

The temperature dependence of the monoclinic lattice constants in the two smectic phases, S¹_G and S²_G, of HxBPA, has been obtained from X-ray diffraction data, in the temperature range 300 K < T < 240 K. The variation of b (unique axis) is consistent with the chain ordering in the S²_G phase indicated by Raman and NMR measurements.     

The local potential approximation for the Brueckner G-matrix and a simple model of the scalar-isoscalar Landau-Migdal amplitude

The Brueckner G-matrix for a slab of nuclear matter is analyzed in the singlet ^1S and triplet ³ S + ³ D channels. The complete Hilbert space is split into two domains, the model subspace S₀, in which the two-particle propagator is calculated explicitly, and the complementary one, S', in which the local potential approximation is used. This kind of local approximation was previously found to be quite accurate for the ^1S pairing problem. A set of model spaces S ₀(E ₀) with different values of the energy E₀ is considered, E₀ being the upper limit for the single-particle energies of the states belonging to S₀. The independence of the G-matrix on E₀ is assumed as a criterion for the validity of the local potential approximation. It turns out that such an independence holds within few percents for E ₀ = 10-20 MeV, for both channels under consideration. The G-matrix within the local potential approximation is used for justifying a simple microscopic model for the coordinate-dependent scalar-isoscalar component f (r) of the Landau-Migdal amplitude in terms of the free T-matrix. Received: 2 November 2001 / Accepted: 4 January 2002     

Damping of the localized surface plasmon polariton resonance of gold nanoparticles

We report on a strong damping of the localized surface plasmon polariton resonance of gold nanoparticles. The ultra-fast dephasing time of localized surface plasmon polariton resonances in gold nanoparticles was systematically studied as a function of the particle size at a fixed photon energy of h ν=1.85 eV. Dephasing times ranging from T₂^expT_{2}^{\mathrm{exp}} = 5.5 fs to 15.0 fs were extracted and an influence of the reduced dimensions was detected. We have identified two dominant damping mechanisms: the well-known surface scattering and, for the first time, band structure changes. We have quantified the influence of these band structure changes on the optical properties by determining the essential damping parameter A to be A ^exp=0.32 nm/fs.     

Effects of L-spin longitudinal quadrupolar relaxation in heteronuclear recoupling and S-spin magic-angle spinning NMR

In experiments on S–L heteronuclear spin systems with evolution of the S-spin magnetization under the influence of a quadrupolar nucleus (L-spin), effects of longitudinal quadrupolar (T_1Q) relaxation of the L-spin coherence on the sub-millisecond time scale have been documented and explored, and methods for minimizing their effect have been demonstrated. The longitudinal relaxation results in heteronuclear dephasing even in the reference signal S₀ of S{L} REDOR, REAPDOR, RIDER, or SPIDER experiments, due to T_1Q-relaxation of the transiently generated S_yL_z coherence, reducing or even eliminating the observable dephasing ΔS. Pulse sequences for measuring an improved reference signal S₀₀ with minimal heteronuclear recoupling but the same number of pulses as for S₀ and S have been demonstrated. From the observed intensity ΔS₀ = S₀₀ − S₀ and the SPIDER signal ΔS/S₀, T_1Q can be estimated. Accelerated decays analogous to the dipolar S₀ curves will occur in T₂ measurements for J-coupled S–L spin pairs. Even in the absence of recoupling pulses, fast T_1Q relaxation of the unobserved nucleus shortens the transverse relaxation time T_2S,MAS of the observed nucleus, in particular at low spinning frequencies, due to unavoidable heteronuclear dipolar evolution during a rotation period. The observed spinning-frequency dependence of T_2S,MAS matches the theoretical prediction and may be used to estimate T_1Q. The effects are demonstrated on several ¹³C{¹⁴N} spin systems, including an arginine derivative, the natural N-acetylated polysaccharide chitin, and a model peptide, (POG)₁₀.     

Ligand‐site exchange in intramolecular complexes of silicon: substituent effects

The intramolecular complexes containing coordination bonds Si←N or Si←O are distinguished for their stereochemical nonrigidity resulting in interconversion between isomers, that is, ligand‐site exchange. The influence of the substituents bound to the silicon atom on the free energies of activation for ligand exchange ΔG^≠ of specific interest is poorly understood. In this work, the literature data on substituent influence on the energies ΔG^≠ for 13 series of the complexes have been considered, using the correlation analysis. On the basis of the obedience of the energies ΔG^≠ to the linear free energy relationship, it has been established for the first time that the ΔG^≠ values depend not only on the inductive and resonance effects but also on the polarizability and steric effects of substituents. The reason for the occurrence of the polarizability effect is the appearance of excess charges on Si and N (or O) atoms as a result of intramolecular coordination consisting in the charge transfer from the donor center (N or O atom) to the acceptor one (Si atom). In some series the contribution of the polarizability or steric effect to the overall change in ΔG^≠ because of the influence of substituents is a maximum. An understanding of these effects may give a better insight into the mechanism of nucleophilic substitution, involving organoelement compounds. Copyright © 2012 John Wiley & Sons, Ltd.     

Effective Action and Phase Transitions in Yang-Mills Theory on Spheres

We study the covariantly constant Savvidy-type chromomagnetic vacuum in finite-temperature Yang-Mills theory on the four-dimensional curved spacetime. Motivated by the fact that a positive spatial curvature acts as an effective gluon mass we consider the compact Euclidean spacetime S ¹ × S ¹ × S ², with the radius of the first circle determined by the temperature a ₁ = (2π T)⁻¹. We show that covariantly constant Yang-Mills fields on S ² cannot be arbitrary but are rather a collection of monopole-antimonopole pairs. We compute the heat kernels of all relevant operators exactly and show that the gluon operator on such a background has negative modes for any compact semi-simple gauge group. We compute the infrared regularized effective action and apply the result for the computation of the entropy and the heat capacity of the quark-gluon gas. We compute the heat capacity for the gauge group SU(2N) for a field configuration of N monopole-antimonopole pairs. We show that in the high-temperature limit the heat capacity per unit volume is well defined in the infrared limit and exhibits a typical behavior of second-order phase transition ~ (T-T_c)^-3/2{\sim(T-T_c)^{-3/2}} with the critical temperature T _c  = (2π a)⁻¹, where a is the radius of the 2-sphere S ².     

Thermoelectric power of the vitreous electrolyte (AgI)0.79(Ag2O.B2O3)0.21

We have determined the thermoelectric power ? of the high ionic conductivity glass (AgI)_0.79(Ag₂O.B₂O₃)_0.21; ? is negative throughout the investigated T range, 320–500 K. The heat of transport of the mobile Ag⁺, Q_Ag, taken as the slope of the straight line fitting ? versus 1/T, is quite lower than the activation energy obtained from conductivity data, viz. Q_Ag = 2.81 kcal/mole^-1 < E_act = 4.34 kcalmole^-1. To circumvent this discrepancy, the analysis of the experimental data is carried out as follows: (i) it is supposed that Q_Ag = E_act in agreement with the free ion theory for solid electrolytes; (ii) the vibrational part of the silver ion entropy, S(Ag⁺, vib), is assumed to be equal to the entropy of silver, S(Ag); (iii) on the ground of a structural model for this kind of glasses, the ideal configurational entropy of the mobile Ag⁺, S(Ag⁺, conf)_id, is evaluated through a statistical approach. The ideal ionic entropy is defined as S(Ag⁺)_id = {S(Ag⁺, vib) + S(Ag⁺, conf)_id}; (iv) the difference {S(Ag⁺)_exp - S(Ag⁺)_id} is viewed as an excess entropy and is described according to the classical model of the regular solutions.