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71.
Afonin AV Ushakov IA Sobenina LN Stepanova ZV Petrova OV Trofimov BA 《Magnetic resonance in chemistry : MRC》2006,44(1):59-65
According to the (1)H, (13)C and (15)N NMR spectroscopic data and ab initio calculations, the strong N--H...O intramolecular hydrogen bond in the Z-isomers of 2-(2-acylethenyl)pyrroles causes the decrease in the absolute size of the (1)J(N,H) coupling constant by 2 Hz in CDCl(3) and by 4.5 Hz in DMSO-d(6), the deshielding of the proton and nitrogen by 5-6 and 15 ppm, respectively, and the lengthening of the N--H link by 0.025 A. The N--H...N intramolecular hydrogen bond in the 2(2'-pyridyl)pyrrole leads to the increase of the (1)J(N,H) coupling constant by 3 Hz, the deshielding of the proton by 1.5 ppm and the lengthening of the N--H link by 0.004 A. The C--H...N intramolecular hydrogen bond in the 1-vinyl-2-(2'-pyridyl)-pyrrole results in the increase of the (1)J(C,H) coupling constant by 5 Hz, the deshielding of the proton by 1 ppm and the shortening of the C--H link by 0.003 A. Different behavior of the coupling constants and length of the covalent links under the hydrogen bond influence originate from the different nature of the hydrogen bonding (predominantly covalent or electrostatic), which depends in turn on the geometry of the hydrogen bridge. The Fermi-contact mechanism only is responsible for the increase of the coupling constant in the case of the predominantly electrostatic hydrogen bonding, whereas both Fermi-contact and paramagnetic spin-orbital mechanisms bring about the decrease of coupling constant in the case of the predominantly covalent hydrogen bonding. 相似文献
72.
Semen S. Sologubov Alexey V. Markin Natalia N. Smirnova Elena S. Chamkina Irina Yu. Krasnova Sergey A. Milenin Olga A. Serenko Zinaida B. Shifrina Aziz M. Muzafarov 《Entropy (Basel, Switzerland)》2021,23(12)
The molar heat capacity of the first-generation hybrid dendrimer with a “carbosilane core/phenylene shell” structure was measured for the first time in the temperature range T = 6–600 K using a precise adiabatic vacuum calorimeter and DSC. In the above temperature interval, the glass transition of the studied compound was observed, and its thermodynamic characteristics were determined. The standard thermodynamic functions (the enthalpy, the entropy, and the Gibbs energy) of the hybrid dendrimer were calculated over the range from T = 0 to 600 K using the experimentally determined heat capacity. The standard entropy of formation of the investigated dendrimer was evaluated at T = 298.15 K. The obtained thermodynamic properties of the studied hybrid dendrimer were compared and discussed with the literature data for some of the first-generation organosilicon and pyridylphenylene dendrimers. 相似文献
73.
Alexander L. Rusanov Zinaida B. Shifrina Elena G. Bulycheva Mukhamed L. Keshtov Marina S. Averina Yulia I. Fogel Klaus Muellen Frank W. Harris 《Macromolecular Symposia》2003,199(1):97-108
The series of new bis(naphthalic anhydrides) was prepared through Diels-Alder cycloaddition. The Diels-Alder cycloaddition was used as a synthetic route to new phenylated monomers as well as to polymers. All polymers synthesized revealed to be soluble in a wide range of organic solvents such as toluene, THF, chloroform, and displayed high thermostability. Therefore, they can be processed easily and are promising candidates for advanced coating systems as well as for electrooptical applications. 相似文献