Conjugated oligomers with terminal donor-acceptor substitution

Conjugated oligomers represent a prominent class of compounds from a viewpoint of their theory, synthesis, and applications in materials science. Push-pull substitution with an electron donor D at one end of the conjugation and an electron acceptor A at the other end results in them having outstanding optical and electronical properties. This Review highlights fundamental synthetic strategies for the preparation of such oligomers with n repeat units (n=1, 2, 3, 4, ..) and the rules that govern their linear and nonlinear optical properties (absorption, frequency doubling and tripling). The unification of chemical, physical, and theoretical aspects with an interdisciplinary image of this class of compounds is attempted herein.     

Investigation of rheological properties of modified phenol-formaldehyde oligomers

Comparative results of determining the rheological properties of modified adhesive compositions based on phenol-formaldehyde oligomer, main wood species, and flax shive are presented. Recommendations on the application of modified glues in the production of composite materials are given.     

The use of furan oligomers for modifying phenol-formaldehyde resin in plywood industry

The modification of phenol-formaldehyde resins by furan oligomers to increase the service characteristics of plywood and plywood products has been suggested. The strength properties, water resistance, fire resistance of plywood based on phenol resin SFZh-3013 modified by furfural-acetone FA monomer at the stage of the mixing of the adhesive composition components have been estimated.     

Molecular and electronic structures of paramagnetic gallium complexes with differently charged o-quinone ligands

Russian Chemical Bulletin - A series of new paramagnetic six-coordinate gallium complexes based on 3,6-di-tert-butyl-o-benzoquinone with N-donor ligands, such as pyridine (Py), 2,2′-dipyridyl...     

Charge recombination in excited donor-acceptor complexes

The influence of the excitation pulse carrier frequency on the dynamics of ultrafast charge recombination in donor-acceptor complexes was studied in the limit of strong electron coupling. An increase in the carrier frequency of excitation pulses invariably decreased the effective rate constant. The dependence of the degree to which the decay of the excited state deviated from the exponential law on reaction exothermicity and the dynamic characteristics of the medium was revealed.     

Some donor-acceptor complexes of silicon phthalocyanine dianions

Studying the reaction of PcSiX₂ (X = Cl, OH) with KOH in DMSO we first discovered red D-A complexes [(Pc²⁻)·PcSiX²] and [(Pc²⁻)·O²] in which silicon phthalocyanine dianion Pc²⁻ is a donor, and the parent phthalocyanine silicon or oxygen are acceptors of electron density. The complexes were characterized by electron absorption, NMR, and ESR spectra. In the reactions with Me₃SiCl, H₂O, or CH₃COOH the complexes regenerate phthalocyanine and O₂. In O₂ atmosphere the [(Pc²⁻)·O₂] complex gradually degrades affording a product of unknown nature.     

Electric conductivity of active carbons from phenol-formaldehyde oligomers and its relationship with the sorption of noble metals

The electric resistance of samples of active carbons, obtained from phenolformaldehyde oligomers of different nature and activated at different conditions, has been investigated. A clear relationship has been found to exist between the specific electric resistance of the carbons and the temperature of their thermal treatment. The structure of the polymer, from which the carbon had been obtained, as well as the nature of the activator affect its electric conductivity. A relationship has been established between the sorption characteristics of carbon sorbents towards substances, absorbed by the carbon, based on a donor-acceptor mechanism, and the electric conductivity of these samples. A symbatic relationship exists between the sorption of [Au(CN)₂]^– and the electric resistance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 4, pp. 508–511, July–August, 1989.     

Charge recombination in excited donor-acceptor complexes with two absorption bands

The dynamics of charge recombination in a photoexcited donor-acceptor complex comprising 1,2,4-trimethoxybenzene (electron donor) and tetracyanoethylene (electron acceptor) in several polar solvents (acetonitrile, valeronitrile, and octanonitrile) was studied in terms of the stochastic approach. The Gibbs energy of charge recombination and the reorganization energies of the medium and quantum and vibrational degrees of freedom were found by fitting the stationary absorption spectrum. The electronic couplings were determined by analyzing the time dependences of the population of the ionic state in acetonitrile. A comparison of the numerical simulation results with the experimental data showed that the nonstationary model under consideration quantitatively described the dynamics of charge recombination and its dependence on the carrier frequency of excitation pulses and the relaxation properties of solvents. Original Russian Text ? V.N. Ionkin, A.I. Ivanov, E. Vauthey, 2009, published in Zhurnal Fizicheskoi Khimii, 2009, Vol. 83, No. 4, pp. 791–797.     

Molecular orbital theory of electron donor-acceptor complexes

A Gaussian basis set consisting of 12s-type, 6p-type and 4d-type functions has been optimized for the third row atoms, together with a 9s, 5p, 3d set for the corresponding dipositive ion. The applicability of these atomic sets for molecular calculation is discussed.

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Zusammenfassung Ein Basissatz von 12s-, 6p- und 4d-Funktionen für die Atome der dritten Reihe des periodischen Systems ist optimalisiert worden; das gleiche gilt für einen entsprechenden Satz für die zweifach positiven Ionen aus 9s-, 5p- und 3d-Funktionen. Ferner wird ihre Anwendbarkeit bei Rechnungen an Molekülen diskutiert.

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Résumé On présente un ensemble optimal de fonctions de base gaussiennes pour les atomes et les ions de la troisième ligne. Cet ensemble est constitué de 12 fonctions du type s, 6 fonctions du type p et 4 fonctions du type d pour l'atome neutre et de 9 fonctions s, 5 fonctions p et 3 fonctions d pour l'ion M²⁺. On discute l'emploi de ces bases pour des calculs moléculaires.

     

Triplet exciton mobilities in weak donor-acceptor complexes

The coupling between neutral and charge-transfer triplet excitons is considered from the viewpoint of its possible influence on triplet exciton migration in alternating stack donor-acceptor complexes. The results are applied for the anthracene-TCNB crystal.     

Photosynthetic reactions in fullerene based donor-acceptor complexes

Donor-acceptor interaction changes essentially the terms of the ground state of binary complexes imparting them a multi-well, in particular, two-well form. A quantum chemical analysis of formation conditions for the amine derivatives of fullerenes depending on the type of the term has been performed by the example of binary complexes, including fullerenes C₆₀ and C₇₀ as acceptors of electrons and amines as donors,. It is found that the addition reaction of amines to fullerene hampered between neutral molecules can occur when the latter are ionized by light.     

Unusual cycloadditions of o-quinone methides with oxazoles

Unusual reactions between various electron-rich oxazoles and ortho-quinone methides is described. This combination leads to some interesting adducts.     

Hydrogenolysis of geminal diazides

The complete hydrogenolysis of compounds containing the geminal diazido functionality is described. Using hydrogen over palladium on charcoal, the diazides are reduced, and primary amines are obtained. For example, aminomalonates and glycines are generated in a straightforward manner. A protocol that provides direct access to acetylated amines derived from 2-amino-1,3-diketones in good to excellent yields, via hydrogenation in the presence of acetic anhydride, is also presented.     

Cyclopentadienylaluminum donor-acceptor complexes - Molecular and supramolecular structure

Lewis acid-base complexes of cyclopentadienylaluminum derivatives Me_xCp_3−x Al (x = 0-2) and trimethylaluminum with selected aromatic amines (L): dmap = 4-dimethylaminopyridine, py-Me = 4-methylpyridyne, were synthesized and characterized by ¹H, ¹³C, ²⁷Al NMR: Cp₃Al · dmap (1), Cp₃Al · py-Me (2), MeCp₂Al · dmap (3), MeCp₂Al · py-Me (4), Me₂CpAl · dmap (5), Me₂CpAl · py-Me (6), Me₃Al · py-Me (7). ¹H NMR studies of 3-6 revealed small amounts of the ligand redistribution products. The crystal structures of 1, 2 and 3 were determined by single X-ray diffraction studies. The compounds 1, 2 and 3 are monomeric with Cp ligands bonded to the aluminum center in η¹(σ), η¹(π) manner. The change of Cp-Al bond character from η¹(π) to η¹(σ) was found to reasonable correlate with the aromaticity of Cp⁻ ligand described by HOMA index. Analysis of close intra- and intermolecular contacts showed presence of CH?π interactions leading to the formation of 2-D supramolecular networks. It was found that these interactions impact on the coordination sphere of aluminum and the conformation of Cp ring.     

Electron paramagnetic resonance of carbon adsorbents from phenol-formaldehyde oligomers and their ability to adsorb noble metals

In order to establish the interrelation between the electronic characteristics of carbons that are manifested in the EPR spectra and their ability to adsorb complex gold and silver ions, the EPR spectra of carbon adsorbents from phenol-formaldehyde resins of various nature, unactivated and activated under various conditions, and the adsorption of [Au(CN)₂]^– and [Ag(CN)₂]^– from cyanide solutions on these same adsorbents were investigated. A parallel relation was observed between the amount of paramagnetic centers on carbon and its adsorption capacity and selectivity in relation to these anions.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 26, No. 6, pp. 742–745, November–December, 1990.