Polarization IR spectra of model crystals containing cyclic NH…S bonded dimers: 2-mercaptothiazoline and 2-mercapto-1-methylimidazole

This paper deals with experimental studies on the polarization IR spectra of hydrogen bonds in 2-mercaptothiazoline and 2-mercapto-1-methylimidazole crystals. The crystal structure of 2-mercaptothiazoline was determined by X-ray diffraction. The polarization spectra of the two compounds were measured in the frequency ranges of the ν_NH and ν_ND bands at 77 and 298 K. The spectra were attributed to cyclic NH…S hydrogen-bond dimers, which are present as structural units in the lattices. Variation of the Davydov-splitting energy magnitude from sample to sample suggests statistical disorder in the crystals. The influence of the electronic properties of the associating small-ring molecules on the spectral properties of the hydrogen bonds is also discussed.     

Derivative analysis of Raman spectra of liquid water in the OH (D) stretching region

Second derivative analysis of Raman spectra of H₂O, D₂O and HOD in liquid phase at room temperature for parallel and perpendicular polarized modes in the OH and OD stretching regions is reported. Five components obtained at approximately 3215, 3375, 3455, 3535 and 3640 cm⁻¹ for the second derivative plots of Raman spectra of liquid water are explained as due to the presence of three types of associated water species with (i) both OH bonds involved in moderately strong hydrogen bonds (SS), (ii) both OH bonds involved in weak hydrogen bonds (WW), and (iii) one OH bond involved in strong and one in weak hydrogen bonds (SW) respectively. The derivative plots obtained for Raman spectra of D₂O and HOD also contain features expected to be present on the basis of this model.     

Intramolecular easily polarizable hydrogen bonds with anilides of 1-piperidine carboxylic acids

IR spectra are plotted from anilides of 1-piperidine carboxylic acids C₅H₁₀N(CH₂)_n CONHC₆H₄R in CHCl₃ and CDCl₃ solutions. In the cases of n = 1 and n = 4, weak intramolecular (NH?N) hydrogen bonds are formed. An asymmetrical energy surface occurs and the proton is present at the N of the anilide group. In the cases of n = 2 and n = 3, intramolecular proton transfer hydrogen bonds of the types N_BH?N_P ? ^?N_B?H⁺N_p are formed. In contrast to the intramolecular OH? N ? O^?1 ? H⁺N bonds with 1-piperidine carboxylic acids, these bonds to not cause IR continua but two bands: one in the region 3250–3190 and one in the region 2500–2450 cm^?1. The fact that, instead of IR continua, bands are observed is explained by the following: (1) these hydrogen bonds are relatively long; (2) they show only a narrow distribution of bond length; (3) the electrical fields at these bonds are small, since they are strongly screened.     

Conformational changes of a calix[8]arene derivative at the air-water interface

The particular behavior of a p-tert-butyl calix[8]arene derivative (C8A) has been studied at the air-water interface using surface pressure-area isotherms, surface potential-area isotherms, film relaxation measurements, Brewster angle microscopy (BAM), and infrared spectroscopy for Langmuir-Blodgett films. Thus, it is observed that the properties of the film, for example, isotherms, domain formation, and FTIR spectra, recorded during the first compression cycle differ appreciably from those during the second compression and following cycles. The results obtained are interpreted on the basis of the conformational changes of the C8A molecules by surface pressure, allowing us to inquire into the inter- and intramolecular interactions (hydrogen bonds) of those molecules. Thus, the compression induces changes in the kind of hydrogen bonds from intra- and intermolecular with other C8A molecules to hydrogen bonds with water molecules.     

几种二醇与非质子溶剂相互作用的红外光谱研究

测定了1，2-乙二醇、1，2-丙二醇、1，4-丁二醇和1，6-己二醇在CCl4中分别与十几种非质子溶剂相互作用的红外光谱，通过考察频率位移的变化，定量地研究了二醇分子内氢键与分子间氢键的协同效应．在四氯化碳介质中，乙二醇、1，2-丙二醇和1，4-丁二醇体系中存在明显的氢键协同效应。利用红外光谱数据，估算了常温下二醇分子内缔体与非质子溶剂的交叉缔合常数，其数值大于一元正链醇与相应溶剂的交叉缔合常数．     

Dimerization of the keto tautomer of acetohydroxamic acid-infrared matrix isolation and theoretical study

Dimerization of the keto tautomer of acetohydroxamic acid has been studied using FTIR matrix isolation spectroscopy and DFT(B3LYP)/6-31+G(d,p) calculations. Analysis of CH3CONHOH/Ar matrix spectra indicates formation of two dimers in which two intramolecular CO...HON bonds within two interacting acetohydroxamic acid molecules are retained. A chain dimer I is stabilized by the intermolecular CO...HN hydrogen bond, whereas the cyclic dimer II is stabilized by two intermolecular NH...O(H)N bonds. Twelve vibrations were identified for dimer I and six vibrations for dimer II; the observed frequency shifts show a good agreement with the calculated ones for the structures I and II. Both dimers have comparable binding energies (DeltaE(ZPE)(CP)I, II=-7.02, -6.34 kcal mol-1) being less stable than calculated structures III and IV (DeltaE(ZPE)(CP)III, IV=-9.50, -8.87 kcal mol-1) in which one or two intramolecular hydrogen bonds are disrupted. In the most stable 10-membered cyclic dimer III, two intermolecular CO...HON hydrogen bonds are formed at expense of intramolecular hydrogen bonds of the same type. The formation of the less stable (AHA)2 dimers in the studied matrixes indicates that the formation of (AHA)2 is kinetically and not thermodynamically controlled.     

Insertion reactions of dimethylsilylene: relative reactivity towards oxygenz.sbnd;hydrogen,siliconhydrogen,and siliconz.sbnd;alkoxy bonds

Photochemically-generated dimethylsilylene is found in competition experiments to insert preferentially into oxygenhydrogen bonds of alcohols compared to either siliconhydrogen bonds of silanes or siliconoxygen bonds of alkoxysilanes. This selectivity for OH bonds compared to SiH bonds is quite high in tetrahydrofuran and in dilute hydrocarbon solutions. However, it decreases in more concentrated hydrocarbon solutions. These effects are discussed in terms of aggregation of alcohols, hydrogen bonding, and solvent-mediated dimethylsilylene reactivity.     

Effect of temperature and water content on the structure of 1,2-propanediol and 1,3-propanediol: Near-infrared spectroscopic study

Effect of temperature and water content on the structure of 1,2-propanediol (12PD) and 1,3-propanediol (13PD) in the liquid phase has been studied by Fourier-transform near-infrared (FT-NIR) spectroscopy. In addition, the spectra of both diols in CCl₄ solutions at various concentrations were measured. The experimental spectra were analyzed by two-dimensional (2D) correlation approach and chemometric methods. The present results give no evidence that 12PD form the intramolecular hydrogen bonding. In contrast, significant amounts of 13PD molecules in diluted CCl₄ solution is involved in the intramolecular hydrogen bonding. At higher concentrations the intramolecular hydrogen bonds are broken and replaced by the intermolecular ones. The structure of pure liquid propanediols is determined by the intermolecular hydrogen bonding. Unlike for monohydroxyl alcohols, addition of water to propanediols leads to faster temperature-induced breaking of the hydrogen-bonded associates. However, variation of water content at constant temperature does not influence the structure of both diols. In this respect behavior of propanediols is similar to that of the monohydric alcohols. The molecules of water in the mixtures are hydrogen bonded to the diols and act as a double proton donor. This bonding appears to be stronger than that in bulk water.     

Conformation of the piperidine ring: Part IV. Investigations of 4-tert-butyl-4-hydroxy-2,2,6,6-tetramethylpiperidine derivatives*

Methods of synthesis of 4-tert-butyl-4-hydroxy-2,2,6,6-tetramethylpiperidine(1), 4-tert-butyl-4-hydroxy-1,2,2,6,6-pentamethylpiperidine (2) and 4-tert-butyl-4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl(3) are described. Interaction of the axial hydroxyl group with axial methyl groups in a chair form of these compounds causes a downfield shift of the methyl proton NMR signal of about 0.2 ppm. IR spectra of 1 and 2 indicate a considerable contribution in solution of non-chair forms stabilized by intramolecular hydrogen bonds. In 3 only intermolecular hydrogen bonds were found. The crystal and molecular structure of 2 have been determined by direct methods and refined to R = 0.0468. The molecules exist in the solid state in a chair conformation only. Van der Waals interactions of bulky substituents hinder a close approach of neighbouring molecules necessary for the formation of intermolecular hydrogen bonds.     

Estimates of the energy of intramolecular hydrogen bonds

A method for the estimation of the energy of intramolecular hydrogen bonds in conjugated systems existing in a variety of conformations is presented. The method is applied to determine the intramolecular hydrogen bond energy in 3-aminopropenal and 3-aminopropenthial. According to the proposed estimation scheme, the intramolecular H-bond energies are found to be of the order of 5-7 kcal/mol. These results are compared with those obtained by using other estimation schemes as well as with the recent results by other authors. Also, the H-bond energies in dimers and trimers of the two molecules are calculated and compared with the corresponding data for internally hydrogen-bonded monomers. This comparison shows that the bond equalization effect is primarily due to proton donor-proton acceptor proximity. In comparison with intermolecular hydrogen bonds, the rigidity of the chelate skeleton enhances this proximity effect. The same effect can be seen in systems with intermolecular hydrogen bonds, although its magnitude is diminished because of the absence of additional forces which pull the proton donor and proton acceptor groups toward each other. No specific resonance-assisted origin of the intramolecular hydrogen bond energy seems to be needed to elucidate the energetics of these bonds.     

The influence of intramolecular hydrogen bonding on the structure and E ↔ Z photoisomerization of urocanic acid derivatives

The molecular structures and E ? Z photoisomerization reactions of methyl urocanate and several urocanamides were investigated. All of the Z isomers possess intramolecular hydrogen bonds. The intramolecular hydrogen bonds may influence the efficiency of photoisomerization but do not totally inhibit its occurrence. The relative energies of the electronic absorption of the E and Z isomers depends on the mode of hydrogen bonding and are accurately predicted in the case of methyl urocanate using INDO/S-CI calculations. The solvent dependence of the absorption spectra of methyl urocanate can be related to the effects of inter- and intramolecular hydrogen bonding.     

Photochromic crown ether complexes: A Raman spectroscopic study

Resonance and preresonance Raman spectra have been obtained in the region 400–1700 cm⁻¹ for some benzothiazolium and indolinium steryl dyes containing a crown ether ring. Spectra arising from the trans isomers are observed selectively due to the resonance effect, and the principal features can be attributed to modes of the central conjugated PhN⁺CCCPh unit present in each of these molecules. Complex formation between the dye molecules and Mg²⁺ in acetonitrile solution results in intramolecular electron transfer. This is observed in the Raman spectra as a downshift of a band assigned to PhO vibration in the crown ether unit, and upshifts of several bands associated with the PhN⁺CCCPh unit, including the phenyl ring, CC and ⁺NC stretches. The results demonstrate the sensitivity of the Raman spectra to changes in the structure and bonding within these photochromic complexing agents on binding to metal ions, and indicate that they may serve as a useful probe for the complicated photoisomerization and complexation reactions of these interesting systems.     

Investigations on 1-Azabicyclic Compounds. 25. Stereochemistry, Hydrogen Bonds, and Gas-Liquid Chromatography of Pyrrolizidine Alcohols

Data have been summarized of several studies on the separation of isomeric pyrrolizidine alcohols by GLC using liquid polar stationary phases. It was shown that the order of emergence of isomers from the chromatographic column is determined to a significant extent by competition of intermolecular hydrogen bonds formed in the sorbate-sorbent systems and intramolecular hydrogen bonds in the molecules of the same pyrrolizidine alcohols. The preference for one or other type of hydrogen bond depends on the stereochemistry of the pyrrolizidine alcohols. Analysis of the geometric conditions for the formation of intramolecular hydrogen bonds in the investigated compounds in conjunction with chromatographic resolution data enables their configurations to be assigned. The anomalously short retention times of highly strained 5-hydroxyalkyl-3-methylpyrrolizidines are explained by the existence in them of a bicyclic conformation predominantly with a trans linkage and with f avora ble geometric conditions for forming intramolecular hydrogen bonds in them.     

Blue-shifted A-H stretching frequencies in complexes with methanol: the decisive role of intramolecular coupling

The presence of a blue shift of A-H stretching frequencies in intermolecular complexes is directly related to the intramolecular coupling between A-H and vicinal A-X bonds in isolated molecules. The intramolecular coupling between vicinal bonds is the decisive parameter that determines whether a general molecule is a candidate for displaying blue-shifted A-H stretching frequencies in intermolecular complexes, with or without hydrogen bonding. The structures and vibrational spectra of dimeric complexes of methanol with H(2)O, HF, HCN, HNC, HOF, HNO, and HSN are investigated at the MP2/6-311++G(2d,2p) approach. Blue- and red-shifts of the methyl C-H stretches of methanol and the various other A-H stretching frequencies in the complexes can be predicted by normal coordinate analyses of methanol and the partner molecules. It is, hence, suggested that conventional normal coordinate analysis is the appropriate predictive tool to decide beforehand whether a given molecule is a promising candidate for the observation of blue shifts in intermolecular complexes.     

A theoretical investigation on the excited state intramolecular single or double proton transfer mechanism of a salicyladazine system

Given the tremendous potential applications of excited state intramolecular proton transfer (ESIPT) systems, ESIPT molecules have received widespread attention. In this work, based on density functional theory (DFT) and time‐dependent DFT (TDDFT) methods, we theoretically study the excited state dynamical behaviors of salicyladazine (SA) molecules. Our simulated results show that the double intramolecular hydrogen bonds of SA are strengthened in the S₁ state via exploring bond distances, bond angles, and infrared (IR) vibrational spectra. Exploring the frontier molecular orbitals (MOs), we confirm that charge redistributions indeed have effects on excited state dynamical behaviors. The increased electronic densities on N atoms and the decreased electronic densities on O atoms imply that charge redistribution may trigger the ESPT process. Analyzing the constructed S₀‐state and S₁‐state potential energy surfaces (PESs), we confirm that only the excited state single proton transfer reaction can occur although SA possesses two intramolecular hydrogen bonds. In this work, we clarify the specific ESIPT mechanism, which may facilitate developing novel applications based on the SA system in future.     

Low temperature structural fluorescence spectra of tetrahydroxyanthraquinone adsorbed on silica

Adsorption of TOAQ on the surface of porous (silica gel) and non-porous (aerosil) silica modification does not cause rupture of intramolecular hydrogen bonds (IMHB). The fine structure spectra of TOAQ fluorescence on silica gel contain a set of frequencies that are characteristic of weakly perturbed molecules. A number of new spectral effects appear due to the existence of pores and centres of a nonhydroxyl character. Hydroxyl groups of aerosil take part in formation of intermolecular hydrogen bonding with the TOAQ C=O group. The bond energy of the four OH-groups of the TOAQ molecule changes non-uniformly, and the symmetry of an equilibrium nuclear configuration of TOAQ decreases.     

Structural studies on some 1,3,5,7-tetraazabicyclo-[3.3.1]-nonane derivatives

From a study of the ¹H NMR spectra of a number of 3,7-disubstituted derivatives of 1,3,5,7-tetraazabicycio - [3.3.1] - nonane it is concluded that these molecules exist in either chair-chair or flattened chair-chair conformations. The derivatives containing COCH₃ and NO substitutents have room temperature spectra consistent with restricted rotation about their NC and NN bonds respectively. High temperature spectra reveal an activation energy, for the rotational barrier of the NC bond in the diacetyl derivative, of 23±2K.Cal/mol.     

Interplay between hydrogen-bond formation and multicenter pi-electron delocalization: intramolecular hydrogen bonds

The specific case of intramolecular hydrogen bonds assisted by pi-electron delocalization is thoroughly investigated using multicenter delocalization analysis. The effect of the pi-electron delocalization on the intramolecular hydrogen-bond strength is determined by means of the relative molecular energies of "open" and "closed" structures, calculated at the B3LYP/6-311++G(d,p) level of theory. These relative energies are compared to variations in the multicenter electron delocalization indices and covalent hydrogen-bond indices, which are shown to correlate very well with the relative strength of the intramolecular hydrogen bonds studied. The multicenter electron delocalization indices and covalent bond indices have been computed using the quantum theory of atoms in molecules approach. The hydrogen bonds are formed with oxygen, nitrogen, or sulfur as acceptor atom, which are also the atoms considered to be bonded to the donor hydrogen. Malonaldehyde is taken as reference; the substitution of oxygen by other atoms at the acceptor and donor positions and the effect of the aromaticity have been studied. The results shown here match perfectly with the qualitative expectations derived from the resonance models. In addition, they provide a quantitative picture of the role played by the pi-electron delocalization on the relative strength of intramolecular hydrogen bonds.     

Biodegradable gemini surfactants. Correlation of area per surfactant molecule with surfactant structure

Values of the area per surfactant molecule of various single chain and gemini quaternary ammonium surfactants containing biodegradable amide and ester groups are obtained from the surface tension measurements and they are mutually compared. It was found that surfactant molecules with the ester group in their structure occupy smaller area at the air/water interface than the corresponding molecules with the amide group, mainly due to the higher conformational flexibility of ester groups. In decreasing the area per surfactant molecule value, hydrogen bonding (both inter- and intramolecular) plays a significant role when amide groups are present in the spacer of a gemini molecule. They must be separated by a polymethylene chain or a flexible group such as cyclohexane which is short enough to allow intramolecular hydrogen bonds. The flexible cyclohexane group with the amide group in single chain surfactants may lead to the formation of intermolecular hydrogen bonds among surfactant molecules which also results in the reduction of the area per surfactant molecule.     

Ultrafast structural dynamics of water induced by dissipation of vibrational energy

In the liquid phase, water molecules form a disordered fluctuating network of intermolecular hydrogen bonds. Using both inter- and intramolecular vibrations as structural probes in ultrafast infrared spectroscopy, we demonstrate a two-stage structural response of this network to energy disposal: vibrational energy from individually excited water molecules is transferred to intermolecular modes, resulting in a sub-100 fs nuclear rearrangement that leaves the local hydrogen bonds weakened but unbroken. Subsequent energy delocalization over many molecules occurs on an approximately 1 ps time scale and is connected with the breaking of hydrogen bonds, resulting in a macroscopically heated liquid.