In 1987-89 were synthesized soluble nano-composites of polyacetylene (NPA) with an abnormally hig... more In 1987-89 were synthesized soluble nano-composites of polyacetylene (NPA) with an abnormally high intensity of Raman scattering and high stability under laser radiation. Here we demonstrate that the key pre-condition to the outstanding characteristics of NPA is the vibrational and rotational mobility of nano-particles, provided by plasticized layers of water on their surface. The results afford a connection between optical properties of NPA and the three-dimensional coherent order arising from self-organization of nanoparticles at synthesis and during film formation. The driving force behind self-organization is the abnormal high vibrational hyper-polarizability of macromolecules leading to coherent dispersive interactions. The principles of synthesis employed can further be used to create 3-D coherently ordered photon crystals and meta-materials.
International Conference on Science and Technology of Synthetic Metals
Summary form only given. The new conjugated polymer poly(tetraphenylquinodimethans) (PTPhQ) with ... more Summary form only given. The new conjugated polymer poly(tetraphenylquinodimethans) (PTPhQ) with degenerate ground state has been obtained in linear (presumably 10) and not-work (presumably 2D) modification by the method of oxidative condensation of diphenylmethane or its chlorine derivatives in the presence of Lewis acids. The PTPhQ has all properties characteristic for conjugated polymers. The neutral form of 1D PTPhQ is soluble and films can be obtained from solutions. Transformation of PTPhQ from neutral to doped form is accompanied by changes in optical spectra and increasing of its conductivity. The doping of PTPhQ by Lewis acids is accompanied by appearance and growth of ESR signal. For example when the 1D PTPhQ is doped by SbCl/sub 5/ the ESR signal with g - value about 2, /spl Delta/ H = 7,2/sup 5/ - 7,9 Gauss and spin concentration more than 10/sup +22/ spins/mo] is observed. The very wide line ( > 5000 Gauss) without fine structure in spectra ESR is also observed.
It has been demonstrated that in IR spectra of vacuum- deposited poly-para-phenylene (PPP) film a... more It has been demonstrated that in IR spectra of vacuum- deposited poly-para-phenylene (PPP) film an extremely strong band at 1375 cm-1 is observed, which is not typical of currently known PPP modifications. High intensity of the band at 1375 cm-1 was associated with the change in the bond order of the 'defect' C-C bond between adjacent quinoid and benzenoid units. Mechanism of quinoid fragments formation in process of PPP film grows is here suggested. The p- phenylene radicals generated during thermal destruction of PPP powder are extremely active. However, when they appear included in the solid phase, they lose much of their initial reactivity, and recombination may be kinetically hindered. In this case, the macromolecules with 'stuck' terminal phenyl radicals could form. The vacuum-deposited poly-para-phenylene solid phase exhibits high crystallinity. Therefore, the recombination of 'stuck' radicals can be essentially hampered. In this case the isomerization of 'stuck' radicals gives delocalized defects. The possibility of practical applications of vacuum-deposited PPP films with delocalized defects is discussed.
Abstract Analysis of the reactivity of the polyene chain and polyacetylene has been carried out b... more Abstract Analysis of the reactivity of the polyene chain and polyacetylene has been carried out by using the reactivity concepts suggested by Dewar, Fukui, Woodward and Hoffmann. It was shown that different types of defects lead to increasing reactivity of the polyene chain. It is suggested that in the absence of defects polyacetylene can be a highly stable material.
1. Crystal silicon with very low concentration of defects was created half a century ago. Advance... more 1. Crystal silicon with very low concentration of defects was created half a century ago. Advances in silicon electronics determined the course of scientific and technical advance for many years. 2. In 1964, professor Little suggested (Phys. Rev 134, A1416) that it might be possible to synthesize a room temperature superconductor using organic materials in which the electrons traveled along certain kinds of chains, effectively confined to one dimension. Above enumerated discoveries led to changes in the general concept of future scientific and technical progress. Unprecedented search of new materials disposing of unique electro-physical and optoelectronic properties began. The ion-radical salts, conjugated polymers, ceramic superconductors and carbon materials were discovered. Scores of thousand articles were published, thousand patents issued and obtained, several hundred start-up companies were set up. According to the expert estimation, total expenses for research in this area am...
New highly-ordered compositions of nanopolyacetylene (NPA) were recently synthesized. These compo... more New highly-ordered compositions of nanopolyacetylene (NPA) were recently synthesized. These compositions are highly stable and could be prepared in the form of solutions, films or fibers. Raman scattering in NPA exhibits high intensity of Stokes and anti-Stokes lines; long sequence of overtones and combination bands; extremely low intensity of fluorescence, and passband in the near-IR region. These properties of trans-NPA compositions suggest many important practical applications of this polymer as key photonic material for development of new types of Raman shifters.
Abstract The influence of polymerization conditions on the electronic structure and concentration... more Abstract The influence of polymerization conditions on the electronic structure and concentration of defects in polyacetylene has been studied. The assumption is that the criterion for high quality polyacetylene is the absence of free polyene chains at all stages during its formation.
In 1987-89 were synthesized soluble nano-composites of polyacetylene (NPA) with an abnormally hig... more In 1987-89 were synthesized soluble nano-composites of polyacetylene (NPA) with an abnormally high intensity of Raman scattering and high stability under laser radiation. Here we demonstrate that the key pre-condition to the outstanding characteristics of NPA is the vibrational and rotational mobility of nano-particles, provided by plasticized layers of water on their surface. The results afford a connection between optical properties of NPA and the three-dimensional coherent order arising from self-organization of nanoparticles at synthesis and during film formation. The driving force behind self-organization is the abnormal high vibrational hyper-polarizability of macromolecules leading to coherent dispersive interactions. The principles of synthesis employed can further be used to create 3-D coherently ordered photon crystals and meta-materials.
International Conference on Science and Technology of Synthetic Metals
Summary form only given. The new conjugated polymer poly(tetraphenylquinodimethans) (PTPhQ) with ... more Summary form only given. The new conjugated polymer poly(tetraphenylquinodimethans) (PTPhQ) with degenerate ground state has been obtained in linear (presumably 10) and not-work (presumably 2D) modification by the method of oxidative condensation of diphenylmethane or its chlorine derivatives in the presence of Lewis acids. The PTPhQ has all properties characteristic for conjugated polymers. The neutral form of 1D PTPhQ is soluble and films can be obtained from solutions. Transformation of PTPhQ from neutral to doped form is accompanied by changes in optical spectra and increasing of its conductivity. The doping of PTPhQ by Lewis acids is accompanied by appearance and growth of ESR signal. For example when the 1D PTPhQ is doped by SbCl/sub 5/ the ESR signal with g - value about 2, /spl Delta/ H = 7,2/sup 5/ - 7,9 Gauss and spin concentration more than 10/sup +22/ spins/mo] is observed. The very wide line ( > 5000 Gauss) without fine structure in spectra ESR is also observed.
It has been demonstrated that in IR spectra of vacuum- deposited poly-para-phenylene (PPP) film a... more It has been demonstrated that in IR spectra of vacuum- deposited poly-para-phenylene (PPP) film an extremely strong band at 1375 cm-1 is observed, which is not typical of currently known PPP modifications. High intensity of the band at 1375 cm-1 was associated with the change in the bond order of the 'defect' C-C bond between adjacent quinoid and benzenoid units. Mechanism of quinoid fragments formation in process of PPP film grows is here suggested. The p- phenylene radicals generated during thermal destruction of PPP powder are extremely active. However, when they appear included in the solid phase, they lose much of their initial reactivity, and recombination may be kinetically hindered. In this case, the macromolecules with 'stuck' terminal phenyl radicals could form. The vacuum-deposited poly-para-phenylene solid phase exhibits high crystallinity. Therefore, the recombination of 'stuck' radicals can be essentially hampered. In this case the isomerization of 'stuck' radicals gives delocalized defects. The possibility of practical applications of vacuum-deposited PPP films with delocalized defects is discussed.
Abstract Analysis of the reactivity of the polyene chain and polyacetylene has been carried out b... more Abstract Analysis of the reactivity of the polyene chain and polyacetylene has been carried out by using the reactivity concepts suggested by Dewar, Fukui, Woodward and Hoffmann. It was shown that different types of defects lead to increasing reactivity of the polyene chain. It is suggested that in the absence of defects polyacetylene can be a highly stable material.
1. Crystal silicon with very low concentration of defects was created half a century ago. Advance... more 1. Crystal silicon with very low concentration of defects was created half a century ago. Advances in silicon electronics determined the course of scientific and technical advance for many years. 2. In 1964, professor Little suggested (Phys. Rev 134, A1416) that it might be possible to synthesize a room temperature superconductor using organic materials in which the electrons traveled along certain kinds of chains, effectively confined to one dimension. Above enumerated discoveries led to changes in the general concept of future scientific and technical progress. Unprecedented search of new materials disposing of unique electro-physical and optoelectronic properties began. The ion-radical salts, conjugated polymers, ceramic superconductors and carbon materials were discovered. Scores of thousand articles were published, thousand patents issued and obtained, several hundred start-up companies were set up. According to the expert estimation, total expenses for research in this area am...
New highly-ordered compositions of nanopolyacetylene (NPA) were recently synthesized. These compo... more New highly-ordered compositions of nanopolyacetylene (NPA) were recently synthesized. These compositions are highly stable and could be prepared in the form of solutions, films or fibers. Raman scattering in NPA exhibits high intensity of Stokes and anti-Stokes lines; long sequence of overtones and combination bands; extremely low intensity of fluorescence, and passband in the near-IR region. These properties of trans-NPA compositions suggest many important practical applications of this polymer as key photonic material for development of new types of Raman shifters.
Abstract The influence of polymerization conditions on the electronic structure and concentration... more Abstract The influence of polymerization conditions on the electronic structure and concentration of defects in polyacetylene has been studied. The assumption is that the criterion for high quality polyacetylene is the absence of free polyene chains at all stages during its formation.
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