Analysis of benzodiaza‐15‐crown‐5 ether derivative binding properties by potentiometric and optical methods

This research concerns the analysis of the binding properties of benzodiaza‐15‐crown‐5 ether derivatives towards different metal ions (Mg(II), Cd(II), Ni(II), Cu(II), Zn(II), Pb(II), Hg(II) and Ag(I)) in acetonitrile and water by potentiometric and optical methods. Benzodiaza‐15‐crown‐5 ether demonstrates high binding affinity towards Hg²⁺ (lg K₁₁ = 12.7), whereas the stability constants of complexes with other studied cations varied from 3 to 6 logarithmic units. Copyright © 2012 John Wiley & Sons, Ltd.     

Radical anions containing the dioxidated 1,2,5‐thiadiazole heterocycle

Radical anions of 3,4‐aryl disubstituted 1,2,5‐thiadiazole 1,1‐dioxide were obtained by chemical and electrochemical reduction of their substrates, and characterized by ESR spectroscopy and cyclic voltammetry. The radical anion of the phenanthro[9,10‐c]‐1,2,5‐thiadiazole 1,1‐dioxide was found to be very stable in an aprotic solvent solution and did not react readily when water was added to the aprotic solvent, or the solution was saturated with oxygen gas. The radical formation chemical reaction competed with nucleophilic addition to the C?N bond of the thiadiazoles. A possible reaction mechanism, and a common reaction intermediate, supported by density functional theory calculations, is presented for the most stable radical. Copyright © 2009 John Wiley & Sons, Ltd.     

Electrogenerated chemiluminescence of benzo 15‐crown‐5 derivatives

Novel electrogenerated chemiluminescence (ECL) reagents C1 , C2 , and C3 with high fluorescence quantum yields bearing 15‐crown‐5 moiety have been synthesized and characterized. The photophysical, electrochemical, and ECL characters of these compounds have been studied in a 1:1 (v/v) PhH/MeCN mixed solvent. The ECL intensity is enhanced distinctly with the increase in the fluorescence quantum yield. Their ECL behaviors have been studied using annihilation and co‐reactant methods (tri‐n‐propylamine (TPrA) was used as a co‐reactant), respectively. The stable ECL emissions of compounds C1 – C3 can be ascribed to the typical and simple monomer ECL emission via S‐route. Copyright © 2008 John Wiley & Sons, Ltd.     

可聚合萘酰亚胺类衍生物的合成及光谱研究

以4-溴-1,8-萘酐和4-硝基-1,8-萘酐为原料制备了分别含碳-碳双键和硅氧烷结构的可聚合萘酰亚胺衍生物4-二甲胺基-1,8-萘酐、4-二甲胺基-N-烯丙基-1,8-萘酰亚胺、4-硝基-N-烯丙基-1,8-萘酰亚胺和4-硝基-N-[(3-三甲氧基硅基)丙基] -1,8-萘酰亚胺. 通过¹H、¹³C及多种二维核磁共振（NMR）技术表征了其分子结构,完成了氢和碳的谱峰归属. 利用紫外吸收光谱与荧光发射光谱研究了这些化合物的光学性质,并讨论了取代基对这些化合物荧光性质的影响.      

Synthesis,characterization, and electrochemical studies of new 5‐ and 6‐nitro N‐acyl‐1H‐indazoles

Two series of new N‐1 acylindazoles containing 5‐ or 6‐nitro groups were synthesized with moderate to good yields and characterized by IR and NMR spectroscopy. Cyclic voltammetry in aprotic media was utilized for the electrochemical characterization of the compounds. The calculated reduction potentials in physiological conditions are similar to those of known commercial antichagasic drugs. Therefore, the novel series reported herein are prospective candidates for antichagasic biological evaluation. Theoretical calculation results indicate that the studied dinitro derivatives undergo a single step reduction process because of the energy proximity of their radical and anionic state. Copyright © 2011 John Wiley & Sons, Ltd.     

The analysis of pH‐dependent protonated conformers of 1‐hydroxyethylidene‐1,1‐diphosphonic acid by means of FT‐Raman spectroscopy,multivariate curve resolution and DFT modelling

1‐Hydroxyethylidene‐1,1‐diphosphonic acid (HEDP) solutions in the pH range 0.98–13.00 were analysed using FT‐Raman spectroscopy and ³¹P and ²³Na NMR spectroscopy. Vibrational bands for different protonated species were observed in the Raman spectra, whereas only a single NMR signal that shifted with pH was observed for all samples over the entire pH range. No significant shift in the ²³Na NMR signal was observed, confirming that formation of Na⁺(aq) complexes did not take place; hence, no interference with the different protonated forms of HEDP occurred. Vibrational bands were assigned using density functional theory(DFT)‐calculated spectra of the most likely conformers in solution. Multivariate curve resolution was performed on the Raman spectra in the region containing the PO stretching vibrations to determine the number of protonated species formed over the entire pH range. Chemometric analysis compares very favourably with the experimental species distribution diagram which was generated using the reported log K_H values. Copyright © 2009 John Wiley & Sons, Ltd.     

Theoretical investigation of two‐photon absorption and fluorescence properties of cypridina luciferin‐based derivatives: 2,3,5‐trisubstituted pyrazine compounds

Two‐photon fluorescent probe materials are significant for achieving observation of living phenomena in entire organs and tissues. To explore new materials with high fluorescence and large two‐photon absorption (TPA) cross section, a series of 2,3,5‐trisubstituted pyrazine derivatives were designed. Their equilibrium geometries, one‐photon absorption, TPA, and luminescence properties have been studied by using density functional theory (DFT), time‐dependent DFT, and Zerner's intermediate neglect of differential overlap program. The results show that the introduction of styrene groups to 2,3,5‐trisubstituted pyrazine derivatives can efficiently increase the conjugated effect and enhance the TPA activity. Moreover, the luminescence properties of 2,3,5‐trisubstituted pyrazine derivatives were compared, and the effect of three substituents on the fluorescence of trisubstituted pyrazine derivatives was analyzed by means of different contribution of the basis functions localized on pyrazine fragment into the highest occupied molecular orbital and lowest unoccupied molecular orbital. The oscillator strengths in the excited state (?_em) for the pyrazine derivatives substituted by styryl are larger than that of other derivatives with acetylamino and indole groups substituted at 2‐site and 5‐site of the pyrazine core, and the ?_em of 3‐indolyl pyrazine derivatives is larger than that of 3‐styrene pyrazine derivatives. It suggests that the styrene group has a great influence on the luminescence property. In addition, the indole group substituted at 3‐site of the pyrazine derivatives can also promote the fluorescence property. Copyright © 2013 John Wiley & Sons, Ltd.     

Electrochemical properties and radical anions of carbocycle‐fluorinated quinoxalines and their substituted derivatives

Electrochemical reduction (ECR) and oxidation (ECO) of 5,6,7,8‐tetrafluoroquinoxaline ( 1 ) and its derivatives bearing various substituents R (7‐H ( 2 ), 7,8‐H₂ (3 ), 6‐CF₃ ( 4 ), 6‐Cl ( 5 ), 5,7‐Cl₂ ( 6 ), 5‐NH₂ ( 7 ), 6‐OCH₃ ( 8 ), 6,7‐(OCH₃)₂ ( 9 ), 6,7,8‐(OCH₃)₃ ( 10 ), 5,6,7,8‐(OCH₃)₄ ( 11 ), 6‐OCH₃,7‐N(CH₃)₂ ( 12 ), 6‐N(CH₃)₂ ( 13 ), 6,7‐(N(CH₃)₂)₂ ( 14 ), 5,6,7‐(N(CH₃)₂)₃ ( 15 ), and 7,8‐cyclo‐(=CF‐CF = CF‐CF=) ( 16 )) in the carbocycle have been studied by cyclic voltammetry in MeCN. For 1 – 4 and 7 – 15 , the first reduction peaks have been found to be 1‐electron and reversible, thus corresponding to the formation of their radical anions (RAs), which are long lived at 295 K except those of 4 – 6 and 15 , 16 . Irreversible hydrodechlorination has been observed for 5 and 6 at the first step of their ECR confirmed by EPR detection of corresponding RAs of 2 and 5,7‐H₂ derivative of 1 ( 17 ) at the next steps. Electrochemically generated RAs of 1 – 3 , 7 – 14 , and 17 have been characterized in MeCN by EPR spectroscopy together with DFT calculations at the (U)B3LYP/6‐31 + G(d) level of theory using PCM to describe the solvent. A noticeable alternation of spin density on the –NCCN– moiety of quinoxaline has been observed for all RAs possessing R‐substitution asymmetry. The comparative electron‐accepting ability of 1 – 15 has been analyzed in terms of their experimental reduction peak potentials and the (U)B3LYP/6‐31 + G(d)‐calculated gas‐phase first adiabatic electron affinities (EAs). The differences in electron transfer solvation energies for 1 – 15 have been evaluated on the basis of ECR peaks' potentials and calculated gas‐phase EAs. The ECO of 1 – 5 and 7 – 14 has been found to be irreversible.     

Characterization of X‐ray gas attenuator plasmas by optical emission and tunable laser absorption spectroscopies

X‐ray gas attenuators are used in high‐energy synchrotron beamlines as high‐pass filters to reduce the incident power on downstream optical elements. The absorption of the X‐ray beam ionizes and heats up the gas, creating plasma around the beam path and hence temperature and density gradients between the center and the walls of the attenuator vessel. The objective of this work is to demonstrate experimentally the generation of plasma by the X‐ray beam and to investigate its spatial distribution by measuring some of its parameters, simultaneously with the X‐ray power absorption. The gases used in this study were argon and krypton between 13 and 530 mbar. The distribution of the 2p excited states of both gases was measured using optical emission spectroscopy, and the density of argon metastable atoms in the 1s₅ state was deduced using tunable laser absorption spectroscopy. The amount of power absorbed was measured using calorimetry and X‐ray transmission. The results showed a plasma confined around the X‐ray beam path, its size determined mainly by the spatial dimensions of the X‐ray beam and not by the absorbed power or the gas pressure. In addition, the X‐ray absorption showed a hot central region at a temperature varying between 400 and 1100 K, depending on the incident beam power and on the gas used. The results show that the plasma generated by the X‐ray beam plays an essential role in the X‐ray absorption. Therefore, plasma processes must be taken into account in the design and modeling of gas attenuators.     

Real‐space multiple‐scattering Hubbard model calculations for d‐ and f‐state materials

Calculations are presented of the electronic structure and X‐ray spectra of materials with correlated d‐ and f‐electron states based on the Hubbard model, a real‐space multiple‐scattering formalism and a rotationally invariant local density approximation. Values of the Hubbard parameter are calculated ab initio using the constrained random‐phase approximation. The combination of the real‐space Green's function with Hubbard model corrections provides an efficient approach to describe localized correlated electron states in these systems, and their effect on core‐level X‐ray spectra. Results are presented for the projected density of states and X‐ray absorption spectra for transition metal‐ and lanthanide‐oxides. Results are found to be in good agreement with experiment.     

A three‐crystal spectrometer for high‐energy resolution fluorescence‐detected X‐ray absorption spectroscopy and X‐ray emission spectroscopy at SSRF

A Johann‐type spectrometer for the study of high‐energy resolution fluorescence‐detected X‐ray absorption spectroscopy, X‐ray emission spectroscopy and resonant inelastic X‐ray scattering has been developed at BL14W1 X‐ray absorption fine structure spectroscopy beamline of Shanghai Synchrotron Radiation Facility. The spectrometer consists of three crystal analyzers mounted on a vertical motion stage. The instrument is scanned vertically and covers the Bragg angle range of 71.5–88°. The energy resolution of the spectrometer ranges from sub‐eV to a few eV. The spectrometer has a solid angle of about 1.87 × 0^?3 of 4π sr, and the overall photons acquired by the detector could be 10⁵ counts per second for the standard sample. The performances of the spectrometer are illustrated by the three experiments that are difficult to perform with the conventional absorption or emission spectroscopy. Copyright © 2016 John Wiley & Sons, Ltd.     

Theoretical studies on the electronic and optical properties of arene‐ versus fluoroarene‐thiophene co‐oligomer

A series of regiochemically varied and core size extension‐modulated arene‐ and fluoroarene‐thiophene co‐oligomers and the unsubstituted sexithiophene α6T were investigated theoretically to explore their electronic and optical properties. These phenylene‐thiophene oligomers show great potential for application in organic light‐emitting diodes (OLEDs), organic diode lasers, and organic thin‐film transistors (OTFTs) because of their feasible tuning of optical and electronic properties by the various structural tunings. Density functional theory (DFT) and the ab initio HF were employed to investigate the geometric and electronic structures of the oligomers in the ground state, and the singles configuration interaction (CIS) methods were used to study the lowest singlet excited state. The lowest excitation energies (E_gs), the radiative lifetime τ, and the maximal absorption/emission wavelength of the oligomers were studied within time‐dependent DFT (TDDFT). All calculations were performed using the 6‐31G(d) basis set. The results show that the HOMOs, LUMOs, energy gaps, ionization potentials (IPs), electron affinities (EAs), and reorganization energies are significantly affected by the various structural tunings in these co‐oligomers, which is important for the improvement of the hole and electron injection into OLEDs. Interestingly, the LUMO energy of 1b , 2b , and 3b is lower than that of α6T and 1a , 2a , 3a by about 0.12 ～ 0.47 eV, indicating that the fluorophenyl‐substitution has significantly improved the electron injection properties of the oligomers. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis and third-order optical nonlinearities of nickel complexes of 8-hydroxyquinoline derivatives

A nickel complex of 5-(acrylamido)methyl-8-hydroxyquinoline, bis-(5-(acrylamido)methyl-8-hydroxyquinolino) nickel(II) (Ni(AAMQ)₂) has been synthesized and its third-order nonlinear optical properties was investigated with respect to that of bis-(8-hydroxyquinolino) nickel(II) (NiQ₂) by single beam Z-scan technique. The real parts (γ_R) of the molecular second-order hyperpolarizabilities were −6.0 × 10⁻⁴⁶ and −5.5 × 10⁻⁴⁶ m⁵/v² for NiQ₂ and Ni(AAMQ)₂, respectively, indicative of similar nonlinear refraction both in sign and in magnitude. After substitution of an acrylamidomethyl group to the 8-hydroxyquinoline (8-HQ) ligand, the nonlinear absorption coefficient of Ni(AAMQ)₂ was enhanced by more than two times. The corresponding imaginary part (γ_I) of the molecular second-order hyperpolarizability was 3.4 × 10⁻⁴⁶ m⁵/v² for Ni(AAMQ)₂ while 1.6 × 10⁻⁴⁶ m⁵/v² for NiQ₂. The increase in nonlinear absorption was attributed to the substitution effect and the enhanced transition dipole moment due to the participation of δ-donor group of CH₂ in the molecular conjugation.     

Conformational analysis of 3‐methyl‐3‐silathiane and 3‐fluoro‐3‐methyl‐3‐silathiane

The conformational equilibria of 3‐methyl‐3‐silathiane 5 , 3‐fluoro‐3‐methyl‐3‐silathiane 6 and 1‐fluoro‐1‐methyl‐1‐silacyclohexane 7 have been studied using low temperature ¹³C NMR spectroscopy and theoretical calculations. The conformer ratio at 103 K was measured to be about 5 _ax: 5 _eq = 15:85, 6 _ax: 6 _eq = 50:50 and 7 _ax: 7 _eq = 25:75. The equatorial preference of the methyl group in 5 (0.35 kcal mol^?1) is much less than in 3‐methylthiane 9 (1.40 kcal mol^?1) but somewhat greater than in 1‐methyl‐1‐silacyclohexane 1 (0.23 kcal mol^?1). Compounds 5–7 have low barriers to ring inversion: 5.65 (ax → eq) and 6.0 (eq → ax) kcal mol^?1 ( 5 ), 4.6 ( 6 ), 5.1 (Me_ax → Me_eq) and 5.4 (Me_eq → Me_ax) kcal mol^?1 ( 7 ). Steric effects cannot explain the observed conformational preferences, like equal population of the two conformers of 6 , or different conformer ratio for 5 and 7 . Actually, by employing the NBO analysis, in particular, considering the second order perturbation energies, vicinal stereoelectronic interactions between the Si–X and adjacent C–H, C–S, and C–C bonds proved responsible. Copyright © 2010 John Wiley & Sons, Ltd.     

Self‐assembly of a [2]pseudorotaxane complex by the threading of a nitrobenzimidazol‐based guest on dibenzo‐24‐crown ether host

A new derivative of the previously reported 1,2‐bis(benzimidazol‐2‐yl)ethane motif, cation [1H₂]²⁺, was synthesized under microwave irradiation and fully characterized by solution NMR, high‐resolution mass spectrometry, cyclic voltammetry and X‐ray crystallography. This cation presents a linear geometry and incorporates nitro substituents as electrochemical handles. In solution, cation [1H₂]²⁺, is capable of threading the cavity of dibenzo‐24‐crown‐8 ether host (DB24C8) giving rise to a [2]pseudorotaxane complex [1H₂?DB24C8]²⁺, regardless of the counterion, [CF₃SO₃]^? or [CF₃COO] ^?. The interpenetrated structure of [1H₂?DB24C8]²⁺ was proven by solution NMR and X‐ray crystallography. This host–guest complex is held together by several non‐covalent interactions, such as hydrogen bonding and ion‐dipole. An electrochemical study of [1H₂]²⁺ in the presence of variable amounts of DB24C8 was performed; due to the irreversible redox behavior of cation [1H₂]²⁺, it was not possible to electrochemically control the association/dissociation process with DB24C8. Copyright © 2014 John Wiley & Sons, Ltd.     

Structure and optical properties of lead iodide based two-dimensional perovskite compounds containing fluorophenethylamines

Phenethylammonium-based perovskites, which can be regarded as a semiconductor/insulator multiple quantum well consisting of lead halide semiconductor layers sandwiched between phenethylammonium insulator layers were prepared. To investigate the effects of the electronic state and the orientation of organic insulator layers on the optical properties of layered perovskites, fluorine substituted analogues were also prepared. The structure and optical properties were investigated by the XRD, UV–Vis absorption, and fluorescence measurements. The exciton absorption peak was shifted by the substitution of fluorine atoms in organic ammonium compounds. It became clear that the optical properties of two-dimensional perovskite compounds were controlled by the substitution of fluorine atoms.     

Experimental and theoretical studies on the one‐photon and two‐photon properties of a series of carbazole derivatives containing styrene

Symmetric‐type carbazole derivatives show great potential for application in two‐photon absorption (TPA) materials and organic light‐emitting diodes. The absorption spectra and fluorescence emission spectra of three different N‐alkyl symmetric‐type carbazole derivatives were investigated. The density functional theory (DFT) time‐dependent‐DFT//Becke, three‐parameter, Lee–Yang–Parr/6‐31 G* method has been used to theoretically study one‐photon absorption properties. The computational results are in good agreement with the available experimental values. The two‐photon excited fluorescence of the compounds was surveyed by 120 fs pulse at 790 nm Ti: sapphire laser operating at 1 kHz repetition rate. Two‐photon excited fluorescence was obtained in the range of 380–600 nm, and TPA cross‐sections were calculated. The TPA properties of the series of compounds were investigated by the ZINDO/single and double electronic excitation configuration interaction method. The influence of the chemical structure of the compounds on two‐photon optical properties was discussed. The results show how the different changes in one‐photon absorption and TPA properties on the basis of lengthening the conjugated bridge and the different carbazole N‐alkyl substituents are attributed to the transition dipole moment in the excited process. Copyright © 2011 John Wiley & Sons, Ltd.     

Size‐dependent Raman and infrared studies of PbSe nanoparticles

Micro‐probe Raman and far‐infrared absorption spectroscopies were used to prove the existence of optical phonon modes of PbSe nanoparticles prepared by colloidal chemistry and preliminarily characterized by transmission electron microscopy. To the best of our knowledge, this is the first time that evidence of the surface phonon (SP) mode by Raman spectroscopy has been experimentally observed. The wavenumber of the SP mode is consistent with its prediction by a dielectric continuum model. While for different PbSe nanoparticle sizes the observed SP mode does not show any obvious change in its position, there is a clear shift by approximately 4 cm⁻¹ toward higher wavenumber in the appearance of the LO(Γ) in the Raman spectra from the 3 nm to the 7 nm PbSe nanoparticles. Far‐infrared measurements demonstrate the presence of the transverse optical TO(Γ) and of the coupled phonon modes. Copyright © 2008 John Wiley & Sons, Ltd.     

NMR and DFT calculation study on structures of 2‐[2‐nitro‐4‐(trifluoromethyl)benzoyl]cyclohexane‐1,3‐dione (NTBC) and its two metabolites isolated from urine of patients suffering from tyrosinemia type I

2‐[2‐Nitro‐4‐(trifluoromethyl)benzoyl]cyclohexane‐1,3‐dione (NTBC) is an active component of nitisinone, a medicine against tyrosinemia type I. Using ¹H, ¹³C and ¹⁹F NMR spectroscopy it has been found that in the urine of patients treated with nitisinone two compounds possessing CF₃ group are always present. They have been isolated by using TLC technique and identified as 4‐hydroxy‐2‐[2‐nitro‐4‐(trifluoromethyl)benzoyl]cyclohexane‐1,3‐dione and 5‐hydroxy‐2‐[2‐nitro‐4‐(trifluoromethyl)benzoyl]cyclohexane‐1,3‐dione, the latter being previously unknown. The constitution, tautomerism and stereochemistry of these compounds have been thoroughly investigated using ¹H and ¹³C NMR spectroscopy supported by theoretical calculations. Molecular structures have been optimized using density functional theory (DFT) with PBE1PBE functional and 6‐31G* basis set. In NMR parameter calculations, the larger 6‐311++G(2d,p) basis set has been used. At both calculation stages, the polarizable continuum model of the solvent has been employed. Copyright © 2010 John Wiley & Sons, Ltd.     

Spectroscopic analysis of a dye–mineral composite–a Raman and FT‐IR study

In this investigation, we address the question of how organic thioindigo binds to inorganic palygorskite to form a pigment similar to Maya Blue. We also address how such binding, if it occurs, might be affected by varying the proportion of dye relative to that of the mineral, and by varying the length of heating time used in preparation of the pigment. In addition to samples of palygorskite and thioindigo both alone, four synthetic pigment samples were prepared; two samples of 8 wt.% dye, one heated at 170 °C for 3 h and one at 170 °C for 9 h, and two samples of 16 wt.% dye, one heated at 170 °C for 3 h and one at 170 °C for 9 h. All samples were examined using Fourier transform‐infrared (FT‐IR) and FT‐Raman spectroscopy. For the pigment samples, FT‐IR peaks at 1627 cm⁻¹ are attributed to a downshifted CO stretching mode of thioindigo due to dye–clay interaction. This interpretation is corroborated by FT‐Raman CO peaks with 14 cm⁻¹ shifts to lower wavenumber for the pigment relative to thioindigo alone. Additional Raman scattering between 550 cm⁻¹ and 650 cm⁻¹ also suggests dye–clay interaction through metal–oxygen bonding. We are thus led to the possibility of mostly hydrogen bonding between silanol and carbonyl at lower dye concentration, with a predominance of metal–oxygen bonding at higher dye concentration. Copyright © 2008 John Wiley & Sons, Ltd.