ChemInform Abstract: APPLICATION OF PHOTOELECTRON SPECTROSCOPY TO INTRAMOLECULARLY HYDROGEN-BONDED SYSTEMS. PART III. THE PHOTOELECTRON SPECTRA OF CIS AND TRANS 2-SUBSTITUTED CYCLOPENTANOLS AND CIS AND TRANS 2-SUBSTITUTED CYCLOHEXANOLS

1976 ◽  
Vol 7 (43) ◽  
pp. no-no
Author(s):  
R. S. BROWN
1976 ◽  
Vol 54 (4) ◽  
pp. 642-646 ◽  
Author(s):  
R. S. Brown

The photoelectron spectra of cis- and trans-2-aminocyclopentanol and cis- and trans-2-(N,N,-dimethylamino)cyclopentanol have been recorded and interpreted. The cis isomers exhibit N lone pair ionizations at higher ionization energy, and O lone pair ionizations at lower ionization energy than their trans isomers.The results are most consistent with the existence and observation of intramolecular hydrogen-bonding in the cis isomers. Infrared data on these systems also show that the cis isomers exist in the intramolecularly hydrogen-bonded state.


1976 ◽  
Vol 54 (12) ◽  
pp. 1929-1937 ◽  
Author(s):  
R. S. Brown

The photoelectron spectra of several well defined molecules exhibiting intramolecular hydrogen bonding has been determined and the analysis of the spectra is in accord with recent molecular orbital calculations of related systems. The experimentally determined enthalpies of the hydrogen bonds in cis-2-aminocyclopentanol and cis- and trans-2-aminocyclohexanol do not correlate in any simple fashion with the shifts in the ionization energies of the nO and nN orbitals compared to a model which precludes hydrogen bonding. The spectral differences attributed to hydrogen bonding in the cis and trans 2-substituted cyclanols cannot be attributed to differences in the through-bond interaction of the n orbitals on either atom since the cis and trans isomers of 1,2-dimethoxycyclopentane and 1,2-dimethoxycyclohexane show virtually identical pe spectra. A discussion of the applicability of Koopmans' theorem and the effect of the hydrogen bond in both the ion and ground states is presented.


1976 ◽  
Vol 54 (20) ◽  
pp. 3203-3205 ◽  
Author(s):  
R. S. Brown

The photoelectron spectra of 2-hydroxycyclohexanone and 2-methoxycyclohexanone, show that the ionization assigned to removal of the carbonyl n-electron is 0.6 eV higher in the former, presumably due to the intramolecular hydrogen bond. The ultraviolet spectra of these molecules also exhibit a marked blue shift of the n → π* transition in the former of roughly 0.5 eV. A discussion of the observations includes consideration of the effect of the intramolecular hydrogen bond on the ground and excited or ion state.


1976 ◽  
Vol 54 (20) ◽  
pp. 3206-3209 ◽  
Author(s):  
R. S. Brown

In an effort to determine the effect of an intramolecular hydrogen bond on the ionization energy of a simple π-system, the photoelectron spectra of syn- and anti-7-norbornenol have been determined. The difference in the ionization energy of the π(C—C) and nÖH orbitals is 0.30 eV for the former, and 0.85 eV for the latter. The photoelectron spectrum of the syn- isomer shows that the π(C—C) bond is roughly 0.2 eV more difficult to ionize than its counter-part in the non-hydrogen bonded geometric isomer and has been interpreted as arising from hydrogen bond induced stabilization of the π-bond. That the spectral differences in the alcohols is not simply due to differing orbital interactions between the two isomers can be demonstrated by the photoelectron spectra of syn- and anti-7-methoxynorbornene. In these systems which allow no possibility of hydrogen bonding the π(C—C) – nÖR difference is the same for both isomers.


1986 ◽  
Vol 64 (4) ◽  
pp. 760-763 ◽  
Author(s):  
Nick Henry Werstiuk ◽  
Douglas Neve Butler ◽  
Sushil Datta

The ultraviolet photoelectron spectra of 2,7-diazatetracyclo[3.3.3.0.4,90.8,11]undecane (1) and its N,N-dimethyl- and methylene-bridged analogues 2 and 3 are documented. The spectrum of 2, which exhibits a nitrogen lone-pair splitting of 0.95 ± 0.1 eV, is interpreted on the basis of an interaction of "inside" lone pairs of the 1,2-diamine. Apparently this is the first report of a study of such an interaction. The spectrum of 1 is consistent with our view that 1 is an intramolecularly hydrogen bonded species in which the lone pairs are "inside–outside".


2018 ◽  
Vol 196 ◽  
pp. 04005
Author(s):  
Irina Stepina ◽  
Irina Kotlyarova

The difficulty of wood protection from biocorrosion and fire is due to the fact that modifiers in use are washed out from the surface of the substrate under the influence of environmental factors. This results in a rapid loss of the protective effect and other practically important wood characteristics caused by the modification. To solve this problem is the aim of our work. Here, monoethanolaminoborate is used as a modifier, where electron-donating nitrogen atom provides a coordination number equal to four to a boron atom, which determines the hydrolytic stability of the compounds formed. Alpha-cellulose ground mechanically to a particle size of 1 mm at most was used as a model compound for the modification. X-ray photoelectron spectra were recorded on the XSAM-800 spectrometer (Kratos, UK). Prolonged extraction of the modified samples preceded the registration of the photoelectron spectra to exclude the fixation of the modifier molecules unreacted with cellulose. As a result of the experiment, boron and nitrogen atoms were found in the modified substrate, which indicated the hydrolytic stability of the bonds formed between the modifier molecules and the substrate. Therefore monoethanolaminoborate can be considered as a non-extractable modifier for wood-cellulose materials.


Author(s):  
Mariola Kądziołka-Gaweł ◽  
Maria Czaja ◽  
Mateusz Dulski ◽  
Tomasz Krzykawski ◽  
Magdalena Szubka

AbstractMössbauer, Raman, X-ray diffraction and X-ray photoelectron spectroscopies were used to examine the effects of temperature on the structure of two aluminoceladonite samples. The process of oxidation of Fe2+ to Fe3+ ions started at about 350 °C for the sample richer in Al and at 300 °C for the sample somewhat lower Al-content. Mössbauer results show that this process may be associated with dehydroxylation or even initiate it. The first stage of dehydroxylation takes place at a temperature > 350 °C when the adjacent OH groups are replaced with a single residual oxygen atom. Up to ~500 °C, Fe ions do not migrate from cis-octahedra to trans-octahedra sites, but the coordination number of polyhedra changes from six to five. This temperature can be treated as the second stage of dehydroxylation. The temperature dependence on the integral intensity ratio between bands centered at ~590 and 705 cm−1 (I590/I705) clearly reflects the temperature at which six-coordinated polyhedra are transformed into five-coordinated polyhedra. X-ray photoelectron spectra obtained in the region of the Si2p, Al2p, Fe2p, K2p and O1s core levels, highlighted a route to identify the position of Si, Al, K and Fe cations in a structure of layered silicates with temperature. All the measurements show that the sample with a higher aluminum content and a lower iron content in octahedral sites starts to undergo a structural reorganization at a relatively higher temperature than the less aluminum-rich sample does. This suggests that iron may perform an important role in the initiation of the dehydroxylation of aluminoceladonites.


Author(s):  
Jemma Gibbard ◽  
Connor Jack Clarke ◽  
Jan RR Verlet

Two-dimensional photoelectron spectroscopy using nanosecond and femtosecond lasers has been used to study the Protopophyrin IX dianion at photon energies between 1.8 - 4.1 eV. The photoelectron spectra indicated the...


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