Trans-cis isomerization of an azoxybenzene liquid crystal

Trans-cis isomerization was investigated in a room temperature liquid crystal mixture of two azoxybenzene compounds. Experiments were performed on isolated molecules in dilute solutions and on the liquid crystal phase composed of the pure compounds. The absorption spectra of the trans and cis isomers were found to be similar to those of azobenzene compounds, as were the birefringence and order parameter of the nematic liquid crystal phase. The photo-optic properties were also similar in that irradiation by ultraviolet light caused the conversion from trans to cis isomers, while short wavelength visible light incident on these compounds resulted in the conversion from cis to trans isomers. The activation energy for thermal relaxation from the cis to trans isomer in the liquid crystal phase was determined to be (66±7) kJ/mole, which is less than for azobenzene in solution. While a photostationary state in a dilute solution with approximately equal numbers of trans and cis isomers was achieved, the nematic-isotropic transition of the mixture of the pure compounds decreased from 70°C to room temperature with a cis concentration of only about 12%. One unusual finding was that the photostationary concentration of trans and cis isomers due to irradiation with light of a specific visible wavelength depended on the starting concentrations of the two isomers, indicating that there may be a molecular conformation that is not photo-responsive and relaxes only thermally.     

The manifestation of non-bonded attraction in the physical properties of cis and trans olefins

Non-bonded attraction is suggested to account for a host of differences in the physical properties of cis and trans olefins of the type XHC=CHX. The main predictions are: (i) The cis isomer is more stable than the trans isomer; (ii) The C=C bond is longer and the C-X bonds are shorter for the cis isomer; (iii) The π MO's orbital energies of the two isomers differ such that the trans isomer is a better electron donor and electron acceptor than the cis isomer. Ab initio calculations at the STO-3G and the 4-31G levels in support of the model are presented. The photoelectron spectra of cis and trans difluoro, dichloro and dibromoethylene are discussed, and found to be in accord with our qualitative model.     

Conformational and NBO analysis on cis and trans isomers of methyl-1-(4-hydroxy-3-methoxyphenyl)-1,2,3,4-tetrahydro-9H-β-carboline-3-carboxylate

The cis and trans-methyl-1-(4-hydroxy-3-methoxyphenyl)-1,2,3,4-tetrahydro-9H-β-carboline-3-carboxylates were prepared and ¹H and ¹³C NMR spectra were recorded for both isomers. Conformational and NBO analysis were carried out for the cis and trans isomers. Conformer structures were pre-optimized using the hybrid method B3LYP along with the 6-311+G(d) basis set. Frequency calculations were employed to confirm the structures as minimum points. Potential energy surfaces (PES) were built at the same level of theory. Geometries obtained from DFT calculations were used to perform NBO analysis by the NBO 3.1 module in GAUSSIAN 03. The results obtained through theoretical calculations revealed that the shielding observed at C1 for the trans isomer can be attributed to carbomethoxy γ-effect, together with the hyperconjugative effect, while only hyperconjugative effects were found to explain the shielding of C3. The higher chemical shift value of C3 of the cis isomer was attributed to the carbonyl substituent, which plays an important role by capturing part of the electronic density in C3.     

Novel starshaped initiators for the controlled radical polymerization based on resorcin[4]- and pyrogallol[4]arenes

Multifunctional macrocyclic initiators for the atom transfer radical polymerization (ATRP) based on different resorcin[4]- and pyrogallol[4]arenes have been synthesized. The initiators with 8, 12 and 16 tertiary -bromoesters on the core were received by complete esterification of all phenolic groups with 2-bromo-isobutyryl bromide. The calixarene derivatives with aliphatic chains on the bridging methine carbon were obtained as their rccc (all cis) isomers, while the corresponding calixarenes with aromatic substituents gave mixtures of their rccc and rctt (cis, cis, trans, trans) isomers.     

Vibrational spectrum and structure of dimethylamino-dichloroarsine

The infrared spectra of solid and gaseous dimethylaminodichloroarsine have been recorded from 4000 to 33 cm⁻¹. The Raman spectra of the liquid and solid phases have also been recorded. A comparison of the Raman spectra of the liquid and solid indicates that there is a change in conformational composition between the two phases. The isomer present at room temperature in the liquid and gas phases is assigned to the trans form. A study of the temperature dependence of the intensities of the Raman spectrum indicates that the trans form is converted to a second isomer which is believed to be the gauche isomer as the temperature is decreased. At −190°C, the Raman intensities indicate that the molecule still exists as a mixture of these two isomers. A vibrational assignment is presented and discussed in detail.     

The synthesis and liquid crystal transition temperatures of some weakly polar nematic trans-4-substituted-cyclohexyl (E)-alk-2-enoates

The effect on the liquid crystal transition temperatures of introducing various groups (for example incorporating C=C, O, CO₂ and CO) into the terminal alkyl chain of a weakly polar model compound 1-[trans-4-(trans-4-propylcyclohexyl)cyclohexyl]pentane has been investigated systematically. Only the compound containing both an ester function and a trans-carbon-carbon double bond exhibited a wide-range nematic mesophase at elevated temperatures. Therefore, a wide variety of trans-4-substituted-cyclohexyl (E)-alk-2-enoates incorporating a carbon double bond with a trans-configuration (E) in the terminal alkyl chain has been synthesized. Nearly all the two-ring esters prepared exhibit a nematic phase over a wide temperature range (≤ 100°C) at elevated temperatures (≤ 200°C). The tendency to form smectic mesophases is often low. Comparisons with the corresponding derivatives incorporating either just a carboxy group (COO) or just a carbon-carbon double bond (C=C) in the same positions indicate that synergetic effects lead to broader nematic phases than would otherwise have been expected. The new compounds are easily prepared from known starting materials.     

The active catalytic species and its isomerisation in the catalytic carbonylation of methanol — a density functional study

The Monsanto acetic acid process is one of the most effective ways to produce acetic acid industrially. This process has been studied experimentally but theoretical investigations are so far sparse. In the current work the active catalytic species [Rh(CO)₂I₂]⁻ (1) and its isomerisation has been studied theoretically using the hybrid B3LYP exchange and correlation functional. Similar calculations has been performed for the iridium complex [Ir(CO)₂I₂]⁻ (2) that also is catalytically active in the methanol carbonylation. Experimental work has confirmed the existence of the cis forms of the active catalytic species, but they do not rule out the possibility of the trans isomers. Our gas phase results show that cis-1 has 4.95 kcal/mol lower free energy than trans-1, and cis-2 has 10.39 kcal/mol lower free energy than trans-2. In the case of rhodium, trans-1 can take part to the catalytic cycle but in case of iridium this is not very likely. We have also investigated the possible mechanisms of the cis to trans conversions. The ligand association mechanism gave free energy barrier of 13.7 kcal/mol for the rhodium complex and 19.8 kcal/mol for iridium. Thus the conversion for the rhodium complex is feasible whereas for iridium it is unlikely.     

Multidimensional anharmonic calculation of the vibrational frequencies and intensities for the trans and cis isomers of HONO with the use of normal coordinates

The equilibrium geometry and the potential energy and dipole moment surfaces have been determined for the cis and trans isomers of the HONO molecule by an ab initio Moller–Plesset (MP2) calculation with a wide set of atomic orbitals. The multidimensional anharmonic vibrational Schrodinger equations are solved using the variational method with the Hamiltonian and wave functions written in the normal coordinates of cis and trans isomers. All one- and two-dimensional and a number of three-dimensional vibrational problems are solved to obtain the energy levels and vibrational eigenfunctions. The frequencies and intensities for the fundamental, overtone and some combination bands are determined in good agreement with the available experimental results. The calculation shows the strength of coupling between different vibrational modes and reveals the presence of strong resonances between the (v₁, v₃, v₆) and (v₁, v₃−1, v₆+2) states of cis-HONO. This fact may be important for understanding the energy redistribution between the intermolecular degrees of freedom. The magnitude and direction of vibrationally averaged ground-state dipole moment of both isomers, as well as the direction of transition dipole moments, are in good agreement with the experimental findings. The changes in the values of dipole moment and some geometrical parameters of cis- and trans-HONO on vibrational excitation are also computed.     

Infrared matrix isolation and quantum chemical studies of the nitrous acid complexes with water

The 1:1 and 2:1 complexes between water and trans- and cis-isomers of nitrous acid have been isolated in argon matrices and studied using FTIR spectroscopy and DFT(B3LYP) calculations with a 6-311++G(2d,2p) basis set. The analysis of the experimental spectra indicate that 1:1 complexes trapped in solid argon involve very strong hydrogen bond in which acid acts as the proton donor and water as the proton acceptor. The perturbed OH stretches are −248, −228 cm⁻¹ red shifted from their free-molecules values in complexes formed by trans- and cis-HONO isomers, respectively. The calculated spectral parameters for the two complexes are in good agreement with experimental data. The calculations also predict stability of two more 1:1 weakly bound complexes formed by each isomer. In these the water acts as the proton donor and one of the two oxygen atoms of the acid as the acceptor. The experimental spectra demonstrate also formation of 2:1 complex between water and trans-HONO isomer in an argon matrix. The performed calculations indicate that the complex involves a seven-membered ring in which OH group of HONO forms very strong hydrogen bond with the oxygen atom of one water molecule and nitrogen atom acts as a weak proton acceptor for the hydrogen atom of the second water molecule of the water dimer. The observed perturbations of the OH stretch of trans-HONO (750 cm⁻¹ red shift) is much larger than that predicted by calculations (556 cm⁻¹ red shift); this difference is attributed to strong solvation effect of argon matrix on very strong hydrogen bond.     

Palladium(II) coordination and cyclometallated complexes derived from 1-tert-butylpyrazole

The synthesis and characterization of a number of new coordination compounds of Pd^II with the nitrogen donor 1-tert-butylpyrazole (^tBuPzH) are described. Compounds are trans-[Pd(^tBuPzH)₂Cl₂] and the cyclometallated structures [Pd₂(^tBuPz)₂(AcO)₂] and [Pd₃(^tBuPz)₂(AcO)₄]. All these complexes are mixtures of syn and anti isomers. Also, the chloro-bridged complex [Pd₂(^tBuPz)₂Cl₂] has been isolated as an equilibrium mixture of cis and trans isomers. The compounds have been studied by variable temperature ¹H- and ¹³C-NMR spectroscopy.     

A kinetic study of the thermal rearrangement of 2-(trifluoromethyl)-1-vinylcyclopropane

2-(Trifluoromethyl)-1-vinylcyclopropane (6) has been synthesized and its thermal rearrangement investigated. Both the interconversion of the cis and trans isomers of 6 and its irreversible conversion to a mixture of 3- and 4-(trifluoromethyl)cyclopentenes (1:3.9 ratio) proceeded slower than those of any previously reported 2-substituted vinylcyclopropane. It can be concluded that a trifluoromethyl substituent has little if any effect on C---C bond dissociation energies or upon carbon radical stability.     

Reactivity of ruthenium complexes with uninegative (X,S)-donor ligands (X = S,P)—II. Phosphine substitution in [Ru(S,S)2(PR3)2] derivatives. Crystal structure of trans-bis(O-ethyldithiocarbonate)bis(dimethylphenylphosphine)-ruthenium(II)

The complexes [Ru(S,S)₂(PPh₃)₂] [S,S = EtCOCS₂⁻, (CH₂)₄NCS₂⁻] react with a variety of tertiary phosphines with the substitution of triphenylphosphine and the formation of [Ru(S,S)₂(PR₃)₂]. The reaction occurs with the formation ofthe cis isomer, except for the complex with PMe₂Ph that gives rise to the trans isomer as the crystal structure shows. The effect of the different phosphines on the ruthenium complex is analysed in terms of the spectroscopic and electrochemical properties of the isolated compounds. The cyclic voltammetric studies of the cis complexes show that isomerization to the trans isomer occurs on oxidation. This isomerization is not observed in the trans-[Ru(S,S)₂(PMe₂Ph)₂] complexes that give rise to stable trans-ruthenium(II)/ruthenium(III) couples. In a similar way the diphosphine complexes afford a quasi-reversible cis-ruthenium(II)/ruthenium(III) process.     

Cyclopropyl carbanions derived from esters of 2-phenylcyclopropylcarboxylic acids: Configurational stability and reaction with electrophiles

The base-catalyzed cis-trans isomerization of cis and trans-alkyl 2-phenylcyclopropylcarboxylates was studied in several aprotic solvents. It was found that contact ion-pain of the derived carbanion lithium salts were configurationally more stable than the solvent-separated ones. Reaction of either the cis or the trans esters with MeI, and the reaction of the cis ester with Ph₂C = O, resulted in the corresponding I-substituted derivatives having cis geometry only. This was explained as due to steric hindrance to elctrophilic attack exerted by the 2-phenyl group in the case of the trans substrate. The trans esters did not react with Ph₂C=O. Inhibition of the trans-to-cis isomerization of the carbanion salt of the trans substrate in presence of Ph₂C=O could lead to this result.     

Photodynamics of azobenzene in a hindering environment

We have run trajectory surface hopping simulations of the trans → cis photoisomerization of azobenzene, subject to a pulling force. The model mimics two situations: a trans-azobenzene derivative with bulky substituents that may not be easily displaced, and a recent experiment by Gaub’s group [T. Hugel, N.B. Holland, A. Cattani, L. Moroder, M. Seitz, H.E. Gaub, Science 296 (2002) 1103; N.B. Holland, T. Hugel, G. Neuert, A. Cattani-Scholz, C. Renner, D. Oesterhelt, L. Moroder, M. Seitz, H.E. Gaub, Macromolecules 36 (2003) 2015; G. Neuert, T. Hugel, R.R. Netz, H.E. Gaub, Macromolecules 39 (2005) 789], in which a polymer with azobenzene units was stretched in an atomic force microscope. In both cases, the shortening of the azobenzene moiety in going from the trans to the cis form is opposed by a pulling force. Our simulations show that the trans → cis photoconversion is only partially suppressed by considerably large forces (≈500 pN or more). However, the cis isomer reverts to trans in the ground state, with the help of the pulling force and using the vibrational energy that is available in the first 1–2 ps. The lowering of the quantum yields is therefore the combined result of hindering of the excited state process and of the hot ground state back reaction.     

The Effect Of The Position And Configuration Of Carbon-Carbon Double Bonds On The Mesomorphism Of Thermotropic, Non-Amphiphilic Liquid Crystals

The influence on their mesomorphic behaviour of introducing a carbon-carbon double bond into the chain, central linkage and alicyclic rings in the core of nematic and smectic liquid crystals (LCs) is discussed. Mesogens incorporating a trans-carbon-carbon double bond conjugated with an aromatic ring exhibit high mesophase-isotropic transition temperatures (T_c). However, they are photo-sensitive and can convert to the non-linear, non-mesogenic cis-isomers under the action of light. Non-conjugated double bonds in the terminal chain of mesogens can also lead to higher nematic and smectic C transition temperatures than those of the corresponding materials without a double bond, although the effect is not nearly as great. The position and trans-cis-configuration (E/Z) of the double bond are seen to be decisive. The combination of a hetero-atom (dipole effect) and the added rigidity imposed by the carbon-carbon double bond (steric effect) with a trans-configuration (E) in the terminal alkyl chain attached to the core of a liquid crystal molecule can give rise to a broad nematic phase. The double bond in the terminal chain of nematogens advantageously modifies the elastic constant ratios, as well as other properties of relevance to LCDs, especially for supertwisted TN-LCDs. The double bond in a central linkage gives rise to a broad spectrum of effects, sometimes suppressing undesired smectic phases and widening the nematic phase temperature range. Non-conjugated double bonds in the molecular core in the form of cyclohexene rings generally lead to lower transition temperatures, although smectic phases are sometimes suppressed and a nematic phase is observed. A conjugated double bond in a cyclohexene ring gives rise to a slightly higher T_NI. The effect on the transition temperatures of the double bond in steroid systems is complex.     

Biaxial ordering of terminal diene groups in lipid membranes: an infrared linear dichroism study

The molecular order within the hydrophobic core of membranes of the diene lipid di-tetradecadienoylphosphatidylcholine was studied by means of infrared spectroscopy on multibilayer assemblies which orient macroscopically on the surface of an attenuated total reflection crystal. The relative humidity and temperature were used as variable parameters to demonstrate that there were profound differences in the melting transition of lipids possessing predominantly cis and trans diene groups. The cis isomer undergoes the phase transition at a vapor pressure which is increased by 0.15 GPa when compared with that of the trans isomer. The methylene wagging band progression gives no indication of differences between the acyl chain conformation of the cis and trans forms in the gel state. The frequencies of a number of absorption bands of the diene groups reveal that these moieties are predominantly in the s-trans conformation to accommodate a favorable packing within the bilayer. The linear dichroism of selected in-plane and out-of-plane vibrations of the diene groups gives indications of the biaxial ordering of these moieties. We present the basic equations for the quantitative analysis of IR dichroism data of lamellar structures in terms of transverse and longitudinal molecular order parameters. It turns out that the planes of the rigid diene groups orient preferentially in a perpendicular direction with respect to the bilayer surface and parallel to each other forming in this way a layer of well-aligned diene groups in the bilayer center. This finding is confirmed by the results of X-ray measurements. We suggest that the partial interdigitation of the diene groups of the sn-1 acyl chains promotes the formation of the inverse H_II phase and/or enables the formation of covalent bonds between both the monolayers upon polymerization of diene lipids.     

Deuterium NMR studies of inositol liquid crystals [1]

Deuterium NMR investigations are presented on members of two new mesogenic series derived from the naturally occurring stereoisomers myo- and scW/o-inositol. Tetraethers of these two series exhibit thermotropic columnar phases in which the columns are apparently formed by stacked hydrogen bonded dimers of these molecules which chemically are vicinal diols. Deuterium NMR measurements were performed on the tetraoctyl homologues 2e (a cis diol) and 3e (a trans diol) of these series. We have investigated mixtures of these diols with small amounts of benzene-d₆ as probe molecules as well as samples of the neat diol compounds deuteriated at their hydroxyl groups. The results obtained show that the mesophases of both compounds are uniaxial and align partially in a magnetic field upon slow cooling from their isotropic liquids. The alignment is with the director parallel to the field direction indicating that the anisotropic magnetic susceptibility of this mesophase is positive. The deuterium quadrupole splitting of the benzene-d₆ probe in both systems is temperature dependent and in the trans diol 3e it even changes sign. This is interpreted in terms of a model in which the benzene-d₆ probe equilibrates rapidly between two (or more) solvation sites with quadrupole splittings of opposite signs The deuterium spectra of the neat deuterium labelled cis diol 2e exhibit two different signals due to the two deuterons which are located at the axial and equatorial hydroxyl groups. This indicates that there is no fast intra- or intermolecular exchange of the hydroxyl hydrogens. The overall quadrupole splittings of the hydroxyl deuterons in this compound are highly reduced compared to their static values and this is interpreted in terms of motional modes involving both reorientation of the hydroxyl deuterons about their C-O axis and overall reorientation of the molecules (or pairs of molecules) around the columnar axes. The corresponding spectra of the neat deuteriated trans diol 3e exhibit a single spectrum indicating that both hydroxyl deuterons in this compound are equivalent, or very nearly so. Within the mesophase region the spectrum undergoes gradual changes due to the increase in the molecular mobility, but the overall motional narrowing is less than in the cis isomer 2e. Apparently due to stronger hydrogen bonding in the trans isomer 3e the precession of the hydroxyl groups is hindered and a fast molecular reorientation is only possible at high temperatures.     

Molecular modeling of the olefin metathesis by tungsten(0) carbene complexes

Density functional and second-order Moller–Plesset theory were used to model W(0) carbene mediated homogeneous metathesis reaction of propylene. The calculations show that the rate determining step of the metathesis is the initiation. After the initiation has been completed the rate determining step becomes dissociation of olefin–metallocarbene complex. The low stereoselectivity of the olefin metathesis reaction is due to the close matching of activation energies for cis and trans isomer formation and the fast cis–trans isomerization caused by the catalysts. The non-productive olefin metathesis reaction always dominates the reaction mixture owing to its very low activation energy. The electronic structure of metal carbene olefin complexes can be described as a combination of donor–acceptor interactions between HOMO of the olefin and LUMO of metal carbene located at carbene carbon on the one hand, and the Dewar, Chatt and Duncanson back donation scheme on the other.     

The stereochemistry of Ei reaction of N-p-toluenesulphonyl sulphilimines

The stereochemistry of the pyrolysis of S-alkyl-N-p-tosylsulphilimines was investigated with both the erythro and threo isomers of S-phenyl-S-1-phenyl-2, 2-phenylmethoxy-1-ethyl-N-benzene-sulphonylsulphilimine I_E and I_T. Pyrolyses revealed that I_E gives only trans-1-methoxystilbene V_T in nearly quantitative yield while a mixture of 5·5% trans-V_T and 94·5% cis-V_C are formed from I_T. The kinetics of the reactions of both I_E and I_T obey a good 1st order rate equation. Pyrolysis is considered to proceed via a concerted cis elimination involving a five membered cyclic transition state.     

Construction and investigation of photo-switch property of azobenzene-bridged pillar[5]arene-based [3]rotaxanes

Series of azobenzene-bridged pillar[5]arene-based [3]rotaxanes with different alkyl chain length of guest molecules were constructed by threading-endcapping method with alkylenetriazole as axile and tetrahydrochromene as endcapping group.The encapsulation of pillar[5]arenes were proved by highresolution mass,¹ H NMR and NOESY spectra.The photo-responsive property were examined by irradiation of the synthesized [3]rotaxanes with 365 nm and blue light LED,which caused trans to cis and cis to trans isomerization,respectively.Irradiation of corresponding model guest compounds without pillar[5]arene encapsulation resulted in near completely trans to cis and cis to trans isomerization,indicating the existence of pillar[5]arenes is the determining factor for the comprised photo isomerization efficiency.