Theoretical and Experimental Study of the Conformation and Vibrational Frequencies of N‐Acetyl‐L‐alanine and N‐Acetyl‐L‐alaninate

The vibrational frequencies of N‐acetyl‐L‐alanine (NAAL), its potassium salt (NAALK) and its free anionic form (NAAL^?) are calculated using density functional theory (B3LYP) combined with the 6‐311 + + G(d,p) basis set. The experimental Raman spectrum of solid NAALK and the scaling factors for calculated values are discussed as well. The three species are characterized by intramolecular NH…O hydrogen bonds leading to the formation of a five‐membered ring. As indicated by the intramolecular (N)H…O distances and by the ν(NH) frequencies, the strength of the intramolecular hydrogen bond is ordered as follows: NAAL^? < NAALK < NAAL^?. Owing to their difference in the coupling with other vibrational modes, the in‐plane and out‐of‐plane vibrations do not reflect the strength of the hydrogen bond.     

Thermal Behavior of an Fe(III)‐2,9,16,23‐Tetramidephthalocyanine‐Grafted Poly(N‐Vinylcarbazole)

Abstract

The introduction of 2,9,16,23‐tetramide‐Fe(III)phthalocyanine [Fe(III)taPc] units into phosphorylated poly(N‐vinylcarbazole) yields an amorphous grafted polymer containing free carbazolyl groups, phosphonic acid attached to carbazolyl groups, and grafted Fe(III)taPc units as evidenced by infrared spectroscopy. Several thermal transitions were detected by differential scanning calorimetry (DSC). The thermodegradation of the grafted sample, analyzed by simultaneous thermogravimetry‐differential thermal analysis (TG‐DTA), showed successive endo‐ and exothermal reactions resulting from the development of a cross‐linked structure. To determine kinetic parameters, both isothermal and dynamic experiments were performed at the different steps of the degradation process and theoretical methods were applied.     

Rheological Behavior of Polyarylsulfone 1‐Butyl‐3‐Methylimidazolium Chloride Solutions

Polyarylsufone polymers are engineering thermoplastics that can only be dissolved in polar solvents. We found that polyarylsufone has good solubility in ionic liquid (IL) with IL being a new kind of green solvent; thus, ILs are potential substitutes for conventional molecular solvents. However, the thermodynamics in ionic liquids are different then those in conventional solvents, so ILs as solvents have attracted enormous attention recently. Rheological behavior is an important factor in polymer material processing. The rheological behavior of polyarylsulfone (PASF) in both N, N,‐dimethylacetamide (DMAc) and ionic liquid 1‐butyl‐3‐methylimidazolium chloride [(Bmim) Cl] were studied in this paper as a function of concentration for concentrated solutions. It is interesting that the rheological behavior of the PASF/(Bmim) Cl solution is very different from that of PASF/DMAc solutions. In DMAc, as concentration increases viscosity increases, while the rheological behavior of the PASF/(Bmim) Cl solution exhibits a maximum in the viscosity‐concentration plots.     

Spectral‐Luminescent Properties of 1,1‐Dioctadecyl‐3,3,3'3'‐Tetramethylindodicarbocyanineperchlorate in Binary Solutions

On the basis of investigation of the absorption and luminescence spectra of 1,1dioctadecyl3,3,3'3'tetramethylindodicarbocyanineperchlorate (D307) molecules and their nonamphiphilic analog in binary solutions of dimethylformamide and water of different composition, a mechanism underlying the quenching luminescence of the D307 molecules has been established which is related to the formation of nonluminescent associates. It is shown that the formation of the micelles of sodium dodecylsulfate (SDS) in a binary solution with 99% content of water destroys the associates, the D307 molecules are captured by the micelles, and their mobility in the micelles is limited.     

Influence of N‐Substitution on Electron Spin Resonance (ESR) Behavior of 2‐(2‐Nitrophenyl)‐1H‐benzimidazole Derivatives

Abstract

The synthesis of 2‐(2‐nitrophenyl)‐1H‐benzimidazole (1), 1‐benzoyl‐2‐(2‐nitrophenyl)‐1H ‐benzimidazole (2), and 1‐acetyl‐2‐(2‐nitrophenyl)‐1H‐benzimidazole (3) is reported. Stable radical anions (1 ^·?, 2 ^·?, and 3 ^·?) were generated by chemical reduction in DMSO and studied by ESR spectroscopy. The interpretation of the ESR spectra was done by means of computational simulation process. Hyperfine coupling constants were assigned by comparison with related compounds, and on the basis of calculation based on SCF INDO MO method in the unrestricted Hartree–Fock scheme.     

Holographic Recording Media Based on Poly‐N‐Epoxypropylcarbazole Films Doped with Organic Dyes

A comparative analysis of the recording media based on polyNepoxypropylcarbazole films doped with cationic, anionic, and intraionic organic dyes has been carried out for the purposes of holographic interferometry. It is shown that in the case of application of intraionic dyes recording media have satisfactory information characteristics. The use of anionic and cationic dyes does not give a positive result because of the absence of the photoconductivity effect in the anionic dyes and of the high electrical conductivity of the films on increase of the temperature of the cationic dyes. The effect of longterm storage of a latent image in the films with intraionic dyes makes it possible to use them for recording holograms with several exposures.     

Infrared Spectroscopic Study of N,N‐Dimethylthioformamide Complexes of the Hofmann Type

Four new Hofmanntype complexes, M(DMTF)₂Ni(CN)₄, (where DMTF is dimethylthioformamide, M=Mn, Cd, Co, or Ni) were synthesized and their structure was determined by an elemental analysis and infrared spectroscopy. The IR spectra of DMTF and its nickel tetracyanine complexes with Mn(II), Cd(II), Co(II), and Ni(II) have been investigated within the range 4000–400 cm^–1. The frequency shifts in the metal complexes agree with the assignment of the CS and CN frequencies. The complexes consist of infinite planar polymer layers of |MNi(CN)₄|. Ndimethylthioformamide is coordinated to this layer from above and below; it is a monodentate ligand and is Sbonded through the metal atom in these complexes.     

Theoretical study on structures of Ga3N, GaN3, Ga3N2 and Ga2N3 clusters

The structures of Ga_3N, GaN_3, Ga_3N_2 and Ga_2N_3 clusters are studied using the full-potential linear-muffin-tin-orbital molecular dynamics (FP-LMTO MD) method. Four structures for Ga_3 N, five structures for GaN_3, nine structures for Ga_3N_2 and nine structures for Ga_2N_3 have been obtained. The most stable structures of these clusters are planar ones. A strong dominance of the N－-N bond over the Ga－-N and Ga－-Ga bonds appears to control the structural skeletons, supporting the previous result obtained by Kandalam and co-workers. The most stable structures of these small GaN clusters displayed semiconductor-like properties through the calculation of the HOMO－LUMO gaps.     

Structural Assignment of Isomeric S‐ and S,N‐1‐Alkoxycarbonylalkylated 6‐Amino‐2‐thiouracil Derivatives by Means of 1H and 13C NMR Spectroscopy

Abstract

The structures of new isomeric 2‐alkoxycarbonylalkylthio‐ and 2‐alkoxy‐ carbonylalkylthio‐1‐alkoxycarbonylalkyl‐6‐aminouracils (1–21) have been established on the basis of the ¹H NMR and ¹³C NMR spectroscopic data. The ¹H NMR and ¹³C NMR spectra of 1–21 have been fully assigned by a combination of two‐dimensional experiments [heteronuclear multiple quantum coherence (HMQC) and heteronuclear multiple bond correlation (HMBC)]. The ¹³C NMR spectra have been shown to be able to differentiate between isomers.     

Thermal and Tribological Properties of Fullerene‐Containing Composite Systems. Part 3. Features of the Mechanism of Thermal Degradation of Poly‐(N‐Vinyl‐Pyrrolidone) and Its Compositions with Fullerene C60

By mass‐spectrometric thermal analysis (MTA) the thermochemical features of poly(N‐vinyl pyrrolidone) (PVP) and its compositions with fullerene C₆₀ were studied. The mechanism of PVP thermal degradation was investigated; in particular the nature of the low‐temperature degradation (between 75 and 300°C) accompanied by output of pyrrolidone was explained as well as the influence of fullerene C₆₀ on this mechanism. It was shown that during thermal degradation of copolymer PVP‐C₆₀, there is a disappearance of the low‐temperature peaks of the output of pyrrolidone that is interpreted as an increase of the thermal stability of N‐vinyl‐pyrrolidone fragments in this product in comparison with their thermal stability in pure PVP.     

Structural Characterization of RF‐Sputtered a‐C:N Thin Films by Raman,IR, and X‐ray Reflectometry Spectroscopies

Abstract

Amorphous carbon nitride thin films (a‐C:N) were deposited from a carbon target, at room temperature onto silicon substrates, by reactive RF sputtering in a gas mixture of argon and nitrogen. The structural properties of these films have been studied by Raman, infrared (IR), and X‐ray reflectometry spectroscopies. Both the IR and Raman spectra of the a‐C:N films reveal the presence of C–C, C?C, C?N, and C≡N bonding types. The Raman spectra analysis shows, an increase of the C≡N triple bonds content when the concentration of nitrogen C(N₂) in the gas mixture is increased. The Raman intensities ratio between the disorder (D) and graphitic (G) bands increases with C(N₂) suggesting an increased disorder with the incorporation of nitrogen in the carbon matrix. The effect of C(N₂) on the density of a‐C:N films was also investigated by X‐ray reflectometry measurement. The increase of the nitrogen concentration C(N₂) was found to have a significant effect on the density of the films: as C(N₂) increases from 0 to 100%, the density of the a‐C:N films decreases slightly from 1.81 to 1.62 g/cm³. The low values of density of the a‐C:N films were related (i) to the absence of C–N single bonds, (ii) to the increase of disorder introduced by the incorporation of nitrogen in the carbon matrix, and (iii) to the presence of the bands around 2350 cm^?1 and 3400 cm^?1 associated with the C–O bond stretching modes and the O–H vibration, respectively, suggesting a high atmospheric contamination by oxygen and water. The presence of these bands suggests the porous character of the studied samples.     

Al(N3)3和P(N3)3结构与性质的理论研究

在B3LYP/6-311++G(3df)理论水平,对二元叠氮化合物Al(N3)3和P(N3)3进行密度泛函理论计算研究,获得其稳定分子的几何构型、电子结构、红外光谱以及稳定性。研究结果表明,P(N3)3分子中的磷原子拥有一对孤对电子,给予临近氮原子(Nα)上的孤对电子较大斥力,从而使其表现出三角锥形结构特征,而Al(N3)3表现为平面三角形结构特征。自然键轨道分析表明,Al–Nα和P–Nα键本质上均属于共价键。与叠氮自由基相比较而言,Al(N3)3和P(N3)3的每个叠氮基内部的总成键度显著增大,从而导致N3基的振动频率发生明显蓝移。前线分子轨道能级差和叠氮自由基键离解能的计算结果均表明Al(N3)3比P(N3)3更稳定。     

Al(N3)3和P(N3)3结构与性质的理论研究

在B3LYP/6-311++G(3df)理论水平,对二元叠氮化合物Al(N3)3和P(N3)3进行密度泛函理论计算研究,获得其稳定分子的几何构型、电子结构、红外光谱以及稳定性.研究结果表明,P(N3)3分子中的磷原子拥有一对孤对电子,给予临近氮原子(Nα)上的孤对电子较大斥力,从而使其表现出三角锥形结构特征,而Al(N3)3表现为平面三角形结构特征.自然键轨道分析表明,Al-Nα和P-Nα键本质上均属于共价键.与叠氮自由基相比较而言,Al(N3)3和P(N3)3的每个叠氮基内部的总成键度显著增大,从而导致N3基的振动频率发生明显蓝移.前线分子轨道能级差和叠氮自由基键离解能的计算结果均表明Al(N3)3比P(N3)3更稳定.     

N9H9链状异构体的结构与稳定性的理论研究

采用密度泛函理论(DFT)B3LYP方法,在6-311＋＋G**基组水平上对N9H9可能存在的链状构型进行了几何优化,得到46种稳定链状异构体。应用自然键轨道理论NBO和分子中的原子理论AIM分析了这些化合物的成键特征和相对稳定性,G3MP2方法计算了各异构体的精确能量及在298K时的生成热ΔfHө(298K),并计算了由Peter Politzer等人所介绍的相对比冲量。研究结果表明：各异构体中N原子孤对电子与N＝N形成了p→π共轭作用是影响双键相邻的N－N键长变化的主要原因,并且对异构体的稳定性起着重要作用。所有异构体中N＝N位于链端的稳定性较差,其中B9最稳定, B6稳定性最差;C5是所有异构体中生成热最大的,也是相对比冲量最大的。     

N9H9链状异构体的结构与稳定性的理论研究

采用密度泛函理论(DFT)B3LYP方法,在6-311++G**基组水平上对N9H9可能存在的链状异构体进行了几何优化,得到46种稳定链状异构体.应用自然键轨道理论NBO和分子中的原子理论AIM分析了这些链状异构体的成键特征和相对稳定性,G3MP2方法计算了各异构体的精确能量及在298K时的生成热△fH°(298 K),并计算了由Peter Politzer等人所介绍的相对比冲量.研究蛄果表明:各异构体中N原子孤对电子与N=N形成了P→π共轭作用是影响双键相邻的N-N键长变化的主要原因,并且对异构体的稳定性起着重要作用.所有异构体中N=N位于链端的稳定性较兰,其中B9最稳定,B6稳定性最差;C5是所有异构体中生成热最大的,也是相对比冲量最大的.     

Conformational and Structural Analysis of 6‐(4‐Methoxy‐phenyl)‐1,5,7a‐triphenyl‐tetrahydro‐imidazo[1,5‐b][1,2,4]oxadiazol‐2‐one

Abstract

The cis stereochemistry of 6‐(4‐methoxy‐phenyl)‐1,5,7a‐triphenyl‐tetrahydro‐imidazo[1,5‐b][1,2,4]oxadiazol‐2‐one was studied by use of a PM3 semi‐empirical quantum mechanical model, and x‐ray crystallographic analysis. It crystallizes in the monoclinic space group P2 ₁ /n with a = 10.812(1) Å, b = 16.464(2) Å, c = 13.379(1) Å, α = 90.00°, β = 98.39(1)°, γ = 90.00°, V = 2356.07(4) Å³, Z = 4, D _calc = 1.3067 g cm^?3, F(0 0 0) = 976.41, and μ = 0.086 mm^?1. The structure was solved by direct methods and refined to R = 0.066 for 1257 independent reflections [I > 4σ (I)]. The results from x‐ray diffraction were seen to be generally consistent with the results from previously reported spectroscopic investigations, beside theoretical calculations, except for conformations of five‐membered fused heterocycles. Two inter‐ and intramolecular weak interactions in addition to carbon atoms (C1 and C3) with different chiralities were found in the structure. The conformational study was performed by randomly scanning the potential energy surface belonging to the title compound with respect to selected torsion angles.     

Crystal Structures of Tetrakis‐(4‐chlorophenylthio)‐butatriene and Tetrakis‐(tert‐butylthio)‐butatriene

Tetrakis‐(4‐chlorophenylthio)‐butatriene (3a) and tetrakis‐(tert‐butylthio)‐butatriene (3b) were synthesized, and their crystal structures were determined. The compound 3a is monoclinic, space group P2₁/c, a=6.9785(8), b=8.6803(9), c=22.884(2) Å, β=93.887(6)^o, V=1383.0(3) ų, Z=2. The compound 3b is monoclinic, space group P2₁/n, a=11.0615(6), b=10.8507(4), c=11.2717(6) Å, β =116.427(2)^o, V=1211.5(1) ų, Z=4. The title compounds 3a and 3b reside on an inversion center so that only half of the molecule is crystallographically unique. Both compounds are not planar. The crystal structures of 3a and 3b have cumulated double bonds. The C7–C8–C8ⁱ and C5–C6–C6ⁱ angles that show the linearity in both structures, respectively, are 176.4(3)° in 3a and 175.6(2)° in 3b.     

NMR Studies of Hindered Rotation and Magnetic Anisotropy: The Diels–Alder Adducts of Phencyclone with N‐Phenylmaleimide and N‐(2‐Trifluoromethylphenyl)maleimide. Ab Initio Calculations for Optimized Structures

Abstract

N‐Phenylmaleimide, 2, and N‐(2‐trifluoromethylphenyl)maleimide, 3, were separately added to phencyclone, 1, to yield the corresponding phencyclone Diels–Alder adducts, 4 and 5. The resulting adducts (and some precursors) have been characterized by one‐ and two‐dimensional ¹H and ¹³C NMR at 300 and 75 MHz, and by ¹⁹F NMR at 282 MHz, at ambient temperatures. The NMR data are consistent, for both adducts, with: (a) hindered rotation of the bridgehead unsubstituted phenyl groups about the C(sp²)–C(sp³) bonds, based on slow exchange limit (SEL) spectra and (b) endo adduct configuration based on magnetic anisotropic effects in the ¹H NMR. The NMR spectra of the phencyclone adduct, 4, of N‐phenylmaleimide, indicate free rotation on the NMR timescales (fast exchange limit, FEL spectra) about the N‐phenyl bond. The spectra for the adduct, 5, of N‐(2‐trifluoromethylphenyl)maleimide are interpreted as consistent with SEL regimes, for the N‐aryl rotations, with a single rotamer present in which the trifluoromethyl group is directed “out of” the adduct cavity, and away from the phenanthrenoid moiety. This conclusion is based, in part, on NMR data suggesting the apparent slow N‐aryl bond rotation in a pair of atropisomers corresponding to the acetic acid addition products from the N‐(2‐trifluoromethylphenyl)maleimide. Evidence of magnetic anisotropic effects due to the phenanthrenoid moiety and proximal carbonyls is discussed. ¹H, ¹³C, and ¹⁹F assignments are presented and interpreted. Molecular modeling calculations at the Hartree–Fock level, 6‐31G* basis set, were performed to provide geometry optimizations for energy‐minimized structures of selected compounds.     

Chemical Synthesis of C3N and BC2N Compounds

A chemical reaction for the preparation of B-C-N compounds by using carbon tetrachloride （CC14）, boron tribromide （BBr3）, lithium nitride （Li3N） and sodium as reactants has been carried out at the temperature of 400℃. Measurements of FTIR, XRD, TEM and EELS show that two kinds of compounds have been formed in the prepared sample. One is hollow sphere-like C-N with an amorphous, structure; the other is piece-like polycrystalline B-C-N with the hexagonal structure. Their determined compositions are close to C3N and BC2N, respectively.     

Sin－1N和Sin－2N2（n=3~9）团簇结构与光振动能谱

用密度泛函理论(Density Functional Theory,DFT)的B3LYP/ 6-311G(d)方法,对Sin－1N和Sin－2N2 (n=3~9)团簇的几何构型、总能量、光振动能谱等性质进行了理论研究.通过对基态结构的几何参量分析发现,对Sin－2N2 (n=3~9)团簇,只有在SiN2和Si2N2结构中N-N成键;n＞4团簇结构,N-N不成键.对团簇能量讨论的结果表明;对于Sin－1N (n=3~9)团簇,总原子数是偶数的团簇比奇数的稳定;对于Sin－2N2(n=3~9)团簇,总原子数是奇数的团簇比偶数的稳定.